Research Article, Issue 4
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
Synthesis and identication of meta-(4-bromobenzyloxy)
benzaldehyde thiosemicarbazone (MBBOTSC) as novel
ligand for cadmium extraction by ultrasound assisted-
dispersive-ionic liquid-liquid micro extraction method
Abdolreza Hassanzadeha, Bagher Amirheidarib, Ahmad Salarifarc, Ali Asadipoura and Yaghoub Pourshojaei a,*
a Department of Medicinal Chemistry, Faculty of Pharmacy, Kerman University of Medical Sciences, Kerman, Iran.
b Department of Pharmaceutical Biotechnology, Faculty of Pharmacy, Kerman University of Medical Sciences, Kerman, Iran
c Environmental Engineering, Faculty of Natural Resources, Islamic Azad University, Bandar Abbas Branch, Iran
ABSTRACT
In this research, meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone (MBBOTSC) as a novel ligand was synthesized
from the reaction between meta-(4-bromobenzyloxy) benzaldehyde
and thiosemicarbazide under basic condition in water and ethanol
as solvents. Ligand has the ability to chelate ions and therefore,
it was used to form a complex and extract ions. So, the cadmium
ions in water and wastewater samples were separated based on
MBBOTSC by ultrasound assisted-dispersive-ionic liquid-liquid
microextractionmethod (USA-D-ILLME) before determination
by AT-F-AAS.The MBBOTSC ligand was added to the mixture of
the ionic liquid/acetone(IL/AC, [OMIM][PF6]) and then injected
by syringe to 50 mL of water samples at pH 6-7.The sample was
put into the ultrasonic accessory for 5 minutes, after complexation
(Ligand-Cd; RS…Cd….RS), the water sample was centrifuged for
3 min for phase separation.Due to complexation and back-extraction
of Cd in liquid phase,the amount of Cd ions in the water samples
was determined by AT-F-AAS after dilution eluent (0.5 M, HNO3)
with DW up to 1 mL.In optimized conditions, the Linear ranges
and LOD for 50 mL of water samples were obtained 1-36μg L-1and
0.3μg L-1, respectively (Mean RSD= 1.26%). The validation results
were successfully achieved by spiking real samples and using
electrothermalatomic absorption spectrometry (ET-AAS).
Keywords:
Cadmium,
Meta-(4-bromobenzyloxy)
benzaldehyde thiosemicarbazone,
Ligand,
Synthesis,
Metal extraction,
Ultrasound assisted-dispersive-ionic
liquid-liquid microextraction
ARTICLE INFO:
Received 13 Aug 2021
Revised form 20 Oct 2021
Accepted 19 Nov 2021
Available online 30 Dec 2021
*Corresponding Author: YaghoubPourshojaei
Email: pourshojaei@yahoo.com
https://doi.org/10.24200/amecj.v3.i04.161
------------------------
1. Introduction
Thiosemicarbazones (TSCs) are an important
class of organic compounds containing N and S
elements that have various uses and properties [1].
These compounds as Schiff base ligands have been
widely used to form complexes and to separate
metals [2]. Furthermore, due to the presence
of electron pairs on sulfur and nitrogen, these
compounds are used over a large area (Fig. 1).
TSCs form a prominent class of pharmaceuticals
and biologically active compounds by virtue of
their antimicrobial, antiviral, anti-bovine viral
diarrhea, antiproliferative and antifungal activities
[3-7]. Also, the formation of metal complexes plays
a very important role in the treatment of cancer,
especially since there are reports of the destructive
role of reactive oxygen species in increasing
the antiproliferative activity of chelators against
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-105
93
93
O
Pd
N
S
N
NH
Cl
N
HN NH
2
S
HO
1
An anticancer active thiosemicarbazone [
17
]
2
Pd thiosemicarbazone Complex,
as Catalysts for Cross-Coupling Reactions [
18
]
N
N
Mn
N
H
N
O
S
HN
O
HN
N
NH
S
3
Mn(II) thiosemicarbazide complexe as
electrochemical oxygenreductive catalyst [
19
]
NH
O
N
NH
H
N
S
O
ONO
2
4
Isatin thiosemicarbazone as
anti-corrosive agent for the alloy [
20
]
tumour cells [8]. Synthesis of TSC is performed
in different ways: a) it is a two-step pathway in
which hydrazine reacts with isothiocyanate and
the product with aldehyde or ketone, which leads
to TSCs [9], b) it is the opposite of pathway a, ie
hydrazine rst reacts with aldehydes or ketones
and then the resulting compound reacts with
isothiocyanate [10], c) it is a 4-step process, in
which hydrazine rst reacts with carbon disulde
and the resulting intermediate reacts with methyl
iodide to form methylhydrazine thiocarbamate,
eventually nucleophilic substitution with amines
and a condensation reaction with an aldehyde or
ketone produces TSC [11]. In continuation of our
research on the synthesis of various compounds
[12-15] and recent report introducing penicillamine
as a metal chelator [16], herein, MBBOTSC as
ligand containing sulfur and nitrogen has proposed
as cadmium chelator.
The toxicity of cadmium (Cd) in water is very
important because of the long half-life in the
human body. The high toxicity of cadmium caused
to damage human organs such as kidneys, liver,
lungs and cancer [21,22]. Cadmium is easily
transferred from water to plants/humans and has
also contamination in the environment [23]. The
environmental protection agency (EPA) and Agency
for Toxic Substances and Disease Registry reported
that cadmium values in the waters are usually less
than 5 μg L-1[24]. For healthy people, the mean
cadmium concentration in human serum samples is
less than 0.2 μg L-1[25]. So, the determination of
cadmium in water samples is an important concern
for controlling toxicity [26,27]. The sensitive
techniques such as the electrothermal atomic
absorption spectrometry (ET-AAS) [28], the atom
trap assist to ame atomic absorption spectrometry
and ame atomic absorption spectrometry (AT-F-
AAS, F-AAS) [29], inductively coupled plasma–
atomic emission spectrometry (ICP-AES) using
thiosemicarbazide derivative on alumina [30], and
inductively coupled plasma–mass spectrometry
(ICP-MS) [31], was used for the determination
of cadmium in water and wastewater samples.
However, as a low concentration of cadmium and
high interferences in wastewater samples, sample
preparation before analysis is required. Solid-phase
extraction (SPE) and liquid-liquid micro extraction
(LLME) are preferred to other techniques for ultra-
trace cadmium determination and separation in
water samples [ 32,33].
???? AbdolrezaHassanzadeh et al
Fig. 1. Several TSC drivatives with different application
Synthesis of MBBOTSC ligand for cadmium extraction by IL Abdolreza Hassanzadeh et al
tumour cells [8]. Synthesis of TSC is performed
in different ways: a) it is a two-step pathway in
which hydrazine reacts with isothiocyanate and
the product with aldehyde or ketone, which leads
to TSCs [9], b) it is the opposite of pathway a, ie
hydrazine rst reacts with aldehydes or ketones
and then the resulting compound reacts with
isothiocyanate [10], c) it is a 4-step process, in
which hydrazine rst reacts with carbon disulde
and the resulting intermediate reacts with methyl
iodide to form methylhydrazine thiocarbamate,
eventually nucleophilic substitution with amines
and a condensation reaction with an aldehyde or
ketone produces TSC [11]. In continuation of our
research on the synthesis of various compounds
[12-15] and recent report introducing penicillamine
as a metal chelator [16], herein, MBBOTSC as
ligand containing sulfur and nitrogen has proposed
as cadmium chelator.
The toxicity of cadmium (Cd) in water is very
important because of the long half-life in the
human body. The high toxicity of cadmium caused
to damage human organs such as kidneys, liver,
lungs and cancer [21,22]. Cadmium is easily
transferred from water to plants/humans and has
also contamination in the environment [23]. The
environmental protection agency (EPA) and Agency
for Toxic Substances and Disease Registry reported
that cadmium values in the waters are usually less
than 5 μg L-1[24]. For healthy people, the mean
cadmium concentration in human serum samples
is less than 0.2 μg L-1[25]. So, the determination of
cadmium in water samples is an important concern
for controlling toxicity [26,27]. The sensitive
techniques such as the electrothermal atomic
absorption spectrometry (ET-AAS) [28], the atom
trap assist to ame atomic absorption spectrometry
and ame atomic absorption spectrometry (AT-F-
AAS, F-AAS) [29], inductively coupled plasma–
atomic emission spectrometry (ICP-AES) using
thiosemicarbazide derivative on alumina [30], and
inductively coupled plasma–mass spectrometry
(ICP-MS) [31], was used for the determination
of cadmium in water and wastewater samples.
However, as a low concentration of cadmium and
high interferences in wastewater samples, sample
preparation before analysis is required. Solid-phase
extraction (SPE) and liquid-liquid micro extraction
(LLME) are preferred to other techniques for ultra-
trace cadmium determination and separation in
water samples [ 32,33].
Fig. 1. Several TSC drivatives with different application
94 Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-105
Herein a TSC as ligand containing sulfur and
nitrogen was synthesized in two steps; a) synthesis
of a primary aldehyde; meta-(4-bromobenzyloxy)
benzaldehyde, b) synthesis of nal ligand
meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone (Scheme 1). Then the structure
of the nal ligand was identied by spectroscopic
methods such as NNR and IR as well as TLC and
melting point.
In this study, the ligand structure was identied
by spectroscopic methods such as 1HNMR,
13CNMR, and FTIR as well as melting point.
Thin layer chromatography (TLC) was used to
check the progress of the reaction (ethyl acetate
and n-hexane were used as the mobile phase).
Finally, the mixture of MBBOTSC ligand, IL
and acetone was used for cadmium extraction
based on the USA-D-ILLME procedure at pH 6-7
before determined by the AT-F-AAS. The results
were validated by spiking of water samples and
compared to the ET-AAS.
2. Experimental
2.1. Instrumental Analysis
The atom trap ame atomic absorption
spectrometry (AT-F-AAS) was used for cadmium
determination in water and wastewater samples.
The signal absorption improved by the atom trap
accessory was added to the burner AAS which was
caused to increase the sensitivity of absorption for
cobalt analysis. The limits of detection (LOD) for
AT-FAAS and FAAS were achieved 0.05 and 0.2
mg L-1, respectively. The information of cobalt was
entered to software Avanta (wavelength of 228.8
nm, 3.0 mA and silt of 0.5 nm). The auto-sampler
was used for all samples. The linear range for AT-
FAAS was 0.05-1.8 mg L−1 for cobalt analysis. The
validation of results was checked by electrothermal
atomic absorption spectrophotometer (GBC, Aus)
in water samples (0.2-6.0 μg L−1). The pH of the
water samples was tuned by the buffer solutions of
Merck, Germany before measured by the digital
pH meter (Metrohm, Swiss). The phosphate buffers
have adjusted the pH for 6-7.
2.2. Reagents and Materials
All reagents/starting materials and solvents used in
this study were purchased from commercial suppliers
(Merck AG, Aldrich or Acros Organics). The melting
point was measured on an electrothermal IA9100
melting point apparatus xed at 1°C per minute and
are uncorrected. The reagents of phosphate buffers
(CAS N: 7558-79-4) were prepared from Sigma
Aldrich, Germany. The ionic liquid of 1-methyl-3-
octylimidazolium hexauorophosphate ([OMIM]
[PF6], CAS N: 304680-36-2) was prepared from
Sigma Aldrich, Germany. The calibration standards
containing 1, 5, 10, 20, 25, 35 μg mL-1 Cd standard
solutions were prepared by dissolving 1.0 g of
cadmium nitrate (Cd(NO3)2) in 1 L of deionized
water solution (DW in 2% HNO3). The standard
of Cd solutions was daily made by stock solutions
(1g L-1, 1000 mg L-1) which was diluted by DW up
to one litre (Millipore, USA). Other reagents such
as HCl, HNO3 and acetone were purchased from
Merck, Germany.
2.3. Charactrization
IR spectra were recorded using Nicolet FT-IR
Magna 550 spectrographs (KBr disks). The NMR
spectra were recorded on Bruker 300 spectrometers
in DMSO-d6 as solvent. 1H NMR data are reported
in the following order: Chemical shifts (δ) in part
per million (ppm) downeld from TMS as internal
standard; approximate coupling constant values
(J) in Hertz (HZ); spin multiplicities (s, singlet;
d, doublet; t, triplet. Thin-layer chromatography
(TLC) was performed on pre-coated Silica Gel
F254 plates in ethyl acetate: n-hexane as the mobile
phase, for checking the reactions.
2.4. Synthesis of meta-(4-bromobenzyloxy)
benzaldehyde
The meta-(4-bromobenzyloxy) benzaldehyde was
prepared by reaction of 3-hydroxybenzaldehyde
with 4- bromobenzylchloride in the presence of
K2CO3 as catalyst. The physical and chemical
properties of it, was compared with literature and
its structure was conrmed [34]
95
2.5. Synthesis of MBBOTSC
In a 50 ml round bottom ask equipped with a magnet,
dissolved 0.1 g of NaOH in 5 cc of distilled water, at
rst 1 mmol (0.291 mg) of meta-(4-bromobenzyloxy)
benzaldehyde and then gradually 1 mmol (0.091
g) of thiosemicarbazide was added to the resulting
solution. And the mixture was gently stirred for one
day. Then 5 cc of ethanol was added and reuxed for
one hour. The reaction progress was controlled by
TLC EtOAc/n-hexane (1:3) as eluent. The obtained
sediments were ltered using lter paper and dried
in a vacuum. Then the precipitate was recrystilized
in boiling ethanol. At the end, crystalline product was
ltrated to obtain crystalline pure product (Scheme
1). The structure, yield, melting point of synthesized
compound is given in the Table 1. Also, the FT-IR, 1H
NMR and 13C NMR spectra of the synthesized ligand
are shown in Figures 3 to 5, respectively.
2.6. Procedure of metal extraction
By the USA-D-ILLME procedure, the cadmium
was complexed with the MBBOTSC ligand in
water and wastewater samples. Also, the Co ions
was determined by AT-F--AAS. The MBBOTSC
ligand (0.1 g) added to mixture of [OMIM][PF6] and
acetone (0.2 g: 500 μL) and was injected into 50 mL
of Cd included 1-36 μg L-1. After shaking of samples
(5.0 min), the cobalt ions were extracted with sulfur
and nitrogen groups of MBBOTSC ligand [R-
N: (S:) ……Cd(II)←(:S)N:-R] at pH 6. After the
complexation, the Cd-MBBOTSC was separated
with IL [OMIM][PF6] at the bottom of a PVC
conical tube by centrifuging for 3 min and speed
of 4000 rpm. The water samples were set aside by
auto-sampler (50 mL) and the Cd ios in IL phase
back-extracted by 0.5 mL of HNO3 (0.5M). After
diluted acide phase with DW up to 1.0 mL, the Cd
values was determined by AT-FAAS. The procedure
was shown in Figure 2. The enrichment factor (EF)
based on the slope of calibration curve of Cd in the
proposed procedure (USA-D-ILLME) and standard
method was calculated (m1/m2 =tgα, EF= 49.64).
Table 1. Structure, yield and melting point of ligand
m.p. (lit) Yield (%)Structure Entry
187-189 oC87
N
HN NH
2
S
O
Br
2
???? AbdolrezaHassanzadeh et al
H
2
N
H
NNH
2
S
+
N
HN NH
2
S
B
O
O
Br
O
HO HH
O
O
Br
H
Br
O
56
768
A
meta-(4-bromobenzyloxy) benzaldehyde
meta-(4-bromobenzyloxy)
benzaldehyde thiosemicarbazone
Scheme 1. A) Synthesis of meta-(4-bromobenzyloxy) benzaldehyde 6 B) meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone 8, Reagents and conditions: (a) K2CO3, DMF, 100 ºC; (b) NaOH, H2O, EtOH, reux.
Synthesis of MBBOTSC ligand for cadmium extraction by IL Abdolreza Hassanzadeh et al
2.5. Synthesis of MBBOTSC
In a 50 ml round bottom ask equipped with a magnet,
dissolved 0.1 g of NaOH in 5 cc of distilled water, at
rst 1 mmol (0.291 mg) of meta-(4-bromobenzyloxy)
benzaldehyde and then gradually 1 mmol (0.091
g) of thiosemicarbazide was added to the resulting
solution. And the mixture was gently stirred for one
day. Then 5 cc of ethanol was added and reuxed for
one hour. The reaction progress was controlled by
TLC EtOAc/n-hexane (1:3) as eluent. The obtained
sediments were ltered using lter paper and dried in
a vacuum. Then the precipitate was recrystilized in
boiling ethanol. At the end, crystalline product was
ltrated to obtain crystalline pure product (Scheme
1). The structure, yield, melting point of synthesized
compound is given in the Table 1. Also, the FT-IR,
1H NMR and 13C NMR spectra of the synthesized
ligand are shown in Figures 3 to 5, respectively.
2.6. Procedure of metal extraction
By the USA-D-ILLME procedure, the cadmium
was complexed with the MBBOTSC ligand in
water and wastewater samples. Also, the Co ions
was determined by AT-F--AAS. The MBBOTSC
ligand (0.1 g) added to mixture of [OMIM][PF6] and
acetone (0.2 g: 500 μL) and was injected into 50 mL
of Cd included 1-36 μg L-1. After shaking of samples
(5.0 min), the cobalt ions were extracted with sulfur
and nitrogen groups of MBBOTSC ligand [R-
N: (S:) ……Cd(II)←(:S)N:-R] at pH 6. After the
complexation, the Cd-MBBOTSC was separated
with IL [OMIM][PF6] at the bottom of a PVC
conical tube by centrifuging for 3 min and speed
of 4000 rpm. The water samples were set aside by
auto-sampler (50 mL) and the Cd ios in IL phase
back-extracted by 0.5 mL of HNO3 (0.5M). After
diluted acide phase with DW up to 1.0 mL, the Cd
values was determined by AT-FAAS. The procedure
was shown in Figure 2. The enrichment factor (EF)
based on the slope of calibration curve of Cd in the
proposed procedure (USA-D-ILLME) and standard
method was calculated (m1/m2 =tgα, EF= 49.64).
Scheme 1. A) Synthesis of meta-(4-bromobenzyloxy) benzaldehyde 6 B) meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone 8, Reagents and conditions: (a) K2CO3, DMF, 100 ºC; (b) NaOH, H2O, EtOH, reux.
Table 1. Structure, yield and melting point of ligand
96
3. Results and Discussion
The aim of the present study was to synthesize
the meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone derivative and to conrm its
structure by spectroscopic methods such as FT-
IR, 1H-NMR, and 13C-NMR and use it to separate
and extract the cadmium ions from the water and
wastewater samples before determined by AT-F-
AAS. The meta- (4-bromo benzyloxy) benzaldehyde
reacted with thiosemicarbazide under basic condition
to form the target ligand. Ligand synthesis is based
on a nucleophilic attack of the electron pair of the
free amine of thiosemicarbazide on the carbon of the
carbonyl of aldehyde group, and after removing of a
water molecule from intermediate, an imine bond is
formed and the product is obtained.
3.1. FTIR Analysis
The FT-IR, 1H-NMR, 13C-NMR spectra of
the synthesized ligand analyzed to conrm its
structure. In the FT-IR spectrum of the ligand,
two stretching vibration frequencies in the regions
of 3393 and 3342 cm-1 belong to the NH2 group.
The peak that appearing at the stretching vibration
frequency of 3025 cm-1 is related to the aromatic
CH stretching vibrations of this synthesized
ligand. The peak that has appeared at 1530 cm-1 is
related to the stretching vibration frequency of the
C = N. And the peak appearing at the frequency
1262 cm-1 is correspond to the stretching vibration
frequency of the C = S functional group. The peak
at 834 cm -1 is attributed to the C-Br stretching
vibration (Fig.3).
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Fig.2. Determination of cadmium based on MBBOTSC ligand by the USA-D-ILLME procedure
Fig. 3. FT-IR spectrum of MBBOTSC ligand
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-105
3. Results and Discussion
The aim of the present study was to synthesize
the meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone derivative and to conrm its
structure by spectroscopic methods such as FT-
IR, 1H-NMR, and 13C-NMR and use it to separate
and extract the cadmium ions from the water and
wastewater samples before determined by AT-F-
AAS. The meta- (4-bromo benzyloxy) benzaldehyde
reacted with thiosemicarbazide under basic condition
to form the target ligand. Ligand synthesis is based
on a nucleophilic attack of the electron pair of the
free amine of thiosemicarbazide on the carbon of the
carbonyl of aldehyde group, and after removing of a
water molecule from intermediate, an imine bond is
formed and the product is obtained.
3.1. FTIR Analysis
The FT-IR, 1H-NMR, 13C-NMR spectra of
the synthesized ligand analyzed to conrm its
structure. In the FT-IR spectrum of the ligand,
two stretching vibration frequencies in the regions
of 3393 and 3342 cm-1 belong to the NH2 group.
The peak that appearing at the stretching vibration
frequency of 3025 cm-1 is related to the aromatic
CH stretching vibrations of this synthesized
ligand. The peak that has appeared at 1530 cm-1 is
related to the stretching vibration frequency of the
C = N. And the peak appearing at the frequency
1262 cm-1 is correspond to the stretching vibration
frequency of the C = S functional group. The peak
at 834 cm -1 is attributed to the C-Br stretching
vibration (Fig.3).
3. Results and Discussion
The aim of the present study was to synthesize
the meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone derivative and to conrm its
structure by spectroscopic methods such as FT-
IR, 1H-NMR, and 13C-NMR and use it to separate
and extract the cadmium ions from the water and
wastewater samples before determined by AT-F-
AAS. The meta- (4-bromo benzyloxy) benzaldehyde
reacted with thiosemicarbazide under basic condition
to form the target ligand. Ligand synthesis is based
on a nucleophilic attack of the electron pair of the
free amine of thiosemicarbazide on the carbon of the
carbonyl of aldehyde group, and after removing of a
water molecule from intermediate, an imine bond is
formed and the product is obtained.
3.1. FTIR Analysis
The FT-IR, 1H-NMR, 13C-NMR spectra of
the synthesized ligand analyzed to conrm its
structure. In the FT-IR spectrum of the ligand,
two stretching vibration frequencies in the regions
of 3393 and 3342 cm-1 belong to the NH2 group.
The peak that appearing at the stretching vibration
frequency of 3025 cm-1 is related to the aromatic
CH stretching vibrations of this synthesized
ligand. The peak that has appeared at 1530 cm-1 is
related to the stretching vibration frequency of the
C = N. And the peak appearing at the frequency
1262 cm-1 is correspond to the stretching vibration
frequency of the C = S functional group. The peak
at 834 cm -1 is attributed to the C-Br stretching
vibration (Fig.3).
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Fig.2. Determination of cadmium based on MBBOTSC ligand by the USA-D-ILLME procedure
Fig. 3. FT-IR spectrum of MBBOTSC ligand
3. Results and Discussion
The aim of the present study was to synthesize
the meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone derivative and to conrm its
structure by spectroscopic methods such as FT-
IR, 1H-NMR, and 13C-NMR and use it to separate
and extract the cadmium ions from the water and
wastewater samples before determined by AT-F-
AAS. The meta- (4-bromo benzyloxy) benzaldehyde
reacted with thiosemicarbazide under basic condition
to form the target ligand. Ligand synthesis is based
on a nucleophilic attack of the electron pair of the
free amine of thiosemicarbazide on the carbon of the
carbonyl of aldehyde group, and after removing of a
water molecule from intermediate, an imine bond is
formed and the product is obtained.
3.1. FTIR Analysis
The FT-IR, 1H-NMR, 13C-NMR spectra of
the synthesized ligand analyzed to conrm its
structure. In the FT-IR spectrum of the ligand,
two stretching vibration frequencies in the regions
of 3393 and 3342 cm-1 belong to the NH2 group.
The peak that appearing at the stretching vibration
frequency of 3025 cm-1 is related to the aromatic
CH stretching vibrations of this synthesized
ligand. The peak that has appeared at 1530 cm-1 is
related to the stretching vibration frequency of the
C = N. And the peak appearing at the frequency
1262 cm-1 is correspond to the stretching vibration
frequency of the C = S functional group. The peak
at 834 cm -1 is attributed to the C-Br stretching
vibration (Fig.3).
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Fig.2. Determination of cadmium based on MBBOTSC ligand by the USA-D-ILLME procedure
Fig. 3. FT-IR spectrum of MBBOTSC ligand
Fig.2. Determination of cadmium based on MBBOTSC ligand by the USA-D-ILLME procedure
97
Synthesis of MBBOTSC ligand for cadmium extraction by IL Abdolreza Hassanzadeh et al
3.2. 1H-NMR spectrum
In the 1H-NMR spectrum of the ligand, a single
peak appeared in the region of 11.48 μg mL-1, which
corresponds to hydrogen of NH. Two single peaks in
the regions of 8.27 μg mL-1 and 8.1 μg mL-1 belong
to the two protons NH2, and the single peak appear
at the 8.04 μg mL-1 indicate the CH alkene group.
The three aromatic protons appeared as a doublet
at the 7.5 μg mL-1 with coupling constant (J) 6 Hz.
In the area of 7.45 μg mL-1, a doublet with coupling
constant (J) 6 Hz appeared, which corresponds to
two aromatic protons, as well as in the area of 7.35
μg mL-1, doublet with coupling constant (J ) 6 Hz
has appeared related to two aromatic protons. In the
region 7.03 μg mL-1, a triplet peak has appeared with
coupling constant (J) 6 Hz, which is corresponded
to an aromatic proton. The single peak that appears
in the region of 5.15 μg mL-1 belongs to the two
protons of the OCH2 group. The 13C-NMR spectrum
of this compound also conrms the desired structure
in that the ligand contains 11 types of carbon, which
can be seen in the 13C-NMR spectrum as 11 separate
carbon peaks (Fig.4 and 5).
Representative spectral data
Meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone (X): Cream-shaped crystals, m.p.:
187-189°C; FT-IR (KBr) (νmax, cm-1): 3393 (N-H), 3342 (N-
H), 3160 (N-H), 3025 (C-HAr), 1530 (C=N), 1262 (C=S),
1170 (C-O), and 834 (C-Br). 1H NMR (DMSO-d6, 300 MHz)
δ (ppm):11.48 (1H, s,NH), 8.27 (1H, s, NH), 8.1 (1H, s,NH),
8.04 (1H, s,CH), 7.5 (3H, d, J = 6Hz, CHAr), 7.45 (2H, d, J
= 6Hz, CHAr), 7.35 (2H, d, J = 6Hz, CHAr), 7.03 (1H, t, J =
6Hz CHAr), and 5.15 (2H, s, OCH2). 13C NMR (DMSO-d6, 75
MHz) δ (ppm): 178, 158, 142, 136, 136, 131, 130, 121, 117,
112, and 69.
3.2. 1H-NMR spectrum
In the 1H-NMR spectrum of the ligand, a single
peak appeared in the region of 11.48 μg mL-1, which
corresponds to hydrogen of NH. Two single peaks in
the regions of 8.27 μg mL-1 and 8.1 μg mL-1 belong
to the two protons NH2, and the single peak appear
at the 8.04 μg mL-1 indicate the CH alkene group.
The three aromatic protons appeared as a doublet at
the 7.5 μg mL-1 with coupling constant (J) 6 Hz. In
the area of 7.45 μg mL-1, a doublet with coupling
constant (J) 6 Hz appeared, which corresponds to
two aromatic protons, as well as in the area of 7.35
μg mL-1, doublet with coupling constant (J ) 6 Hz
has appeared related to two aromatic protons. In the
region 7.03 μg mL-1, a triplet peak has appeared with
coupling constant (J) 6 Hz, which is corresponded
to an aromatic proton. The single peak that appears
in the region of 5.15 μg mL-1 belongs to the two
protons of the OCH2 group. The 13C-NMR spectrum
of this compound also conrms the desired structure
in that the ligand contains 11 types of carbon, which
can be seen in the 13C-NMR spectrum as 11 separate
carbon peaks (Fig.4 and 5).
Representative spectral data
Meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone (X): Cream-shaped crystals,
m.p.: 187-189°C; FT-IR (KBr) (νmax, cm-1): 3393 (N-H),
3342 (N-H), 3160 (N-H), 3025 (C-HAr), 1530 (C=N), 1262
(C=S), 1170 (C-O), and 834 (C-Br). 1H NMR (DMSO-d6,
300 MHz) δ (ppm):11.48 (1H, s,NH), 8.27 (1H, s, NH), 8.1
(1H, s,NH), 8.04 (1H, s,CH), 7.5 (3H, d, J = 6Hz, CHAr),
7.45 (2H, d, J = 6Hz, CHAr), 7.35 (2H, d, J = 6Hz, CHAr),
7.03 (1H, t, J = 6Hz CHAr), and 5.15 (2H, s, OCH2). 13C
NMR (DMSO-d6, 75 MHz) δ (ppm): 178, 158, 142, 136,
136, 131, 130, 121, 117, 112, and 69.
???? AbdolrezaHassanzadeh et al
Fig. 4. 1H-NMR spectrum of MBBOTSC ligand
98
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Fig 5. 13C-NMR spectrum of MBBOTSC ligand
Fig.6. The mechanism of extraction between nitrogen and thiol of the MBBOTSC ligand with cobalt ion
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-105
3.3. Mechanism of cobalt extraction
The mechanism of extraction is based on the
interaction of imine nitrogen (=N) and thio (=S)
groups of the MBBOTSC with cadmium ions using
dative/covalent bonding to form stable ve ring.
The mechanism of extraction between nitrogen and
thiol of the MBBOTSC with Cd ions was shown
in Figure 6. The mechanism demonstrates that
MBBOTSC ligand can bind to Cd2+ by complex
formations that are easily eliminated from the
water samples. The sulfur and nitrogen groups in
MBBOTSC ligands caused to easily extracted the
Cd ions from aqueous solutions
3.4. Optimizing of parameters
3.4.1.The effect of pH
The pH of the sample is the main parameter for
cadmium extraction from water and wastewater
samples which was affected oncomplexation.
So, the effect of pH on extraction efciency of
cadmium with MBBOTSC ligand was studied
in different pH between 2 to 11 (Fig.7). The
complexation of sulfur and nitrogen groups with
Cd2+ was depended on the pH of samples. Due to
results, the efcient extraction for Cd ions was
obtained more than 96% at pH of 6.0-7.0 (Cd→:S-R
or :NH2-R). At higher pH (more than 7.5), the
extraction of cadmium was reduced and Cd ions
was precipited [Cd(OH)2]. The mechanism was
depended on the coordination bond between Cd2+
and amine /sulfur groups of MBBOTSC ligand
at optimized pH. In acidic pH, the NH2 and SH
groups of the MBBOTSC ligand are protonated
(+) and complexation decreased. Also, in basic
pH at more than 7.5, the NH2 and SH groups
were deprotonated (-) but the cadmium ions
precipitated. So, the MBBOTSC is favorite ligand
for extraction and determination of cadmium in
water samples by the USA-D-ILLME procedure
at pH 6.5.
Fig. 5.
99
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Fig 5. 13C-NMR spectrum of MBBOTSC ligand
Fig.6. The mechanism of extraction between nitrogen and thiol of the MBBOTSC ligand with cobalt ion
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Fig 5. 13C-NMR spectrum of MBBOTSC ligand
Fig.6. The mechanism of extraction between nitrogen and thiol of the MBBOTSC ligand with cobalt ion
3.3. Mechanism of cobalt extraction
The mechanism of extraction is based on the
interaction of imine nitrogen (=N) and thio (=S)
groups of the MBBOTSC with cadmium ions using
dative/covalent bonding to form stable ve ring.
The mechanism of extraction between nitrogen and
thiol of the MBBOTSC with Cd ions was shown
in Figure 6. The mechanism demonstrates that
MBBOTSC ligand can bind to Cd2+ by complex
formations that are easily eliminated from the
water samples. The sulfur and nitrogen groups in
MBBOTSC ligands caused to easily extracted the
Cd ions from aqueous solutions
3.4. Optimizing of parameters
3.4.1. The effect of pH
The pH of the sample is the main parameter for
cadmium extraction from water and wastewater
samples which was affected oncomplexation.
So, the effect of pH on extraction efciency of
cadmium with MBBOTSC ligand was studied
in different pH between 2 to 11 (Fig.7). The
complexation of sulfur and nitrogen groups with
Cd2+ was depended on the pH of samples. Due
to results, the efcient extraction for Cd ions
was obtained more than 96% at pH of 6.0-7.0
(Cd→:S-R or :NH2-R). At higher pH (more than
7.5), the extraction of cadmium was reduced and
Cd ions was precipited [Cd(OH)2]. The mechanism
was depended on the coordination bond between
Cd2+ and amine /sulfur groups of MBBOTSC
ligand at optimized pH. In acidic pH, the NH2
and SH groups of the MBBOTSC ligand are
protonated (+) and complexation decreased. Also,
in basic pH at more than 7.5, the NH2 and SH
groups were deprotonated (-) but the cadmium ions
precipitated. So, the MBBOTSC is favorite ligand
for extraction and determination of cadmium in
water samples by the USA-D-ILLME procedure
at pH 6.5.
???? AbdolrezaHassanzadeh et al
Fig. 7. The effect of pH on cadmium extraction based on MBBOTSC ligand
by the USA-D-ILLME procedure
Synthesis of MBBOTSC ligand for cadmium extraction by IL Abdolreza Hassanzadeh et al
Fig.6.The mechanism of extraction between nitrogen and thiol of the MBBOTSC ligand with cobalt ions
234566.5 7 8 9 10
100 Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-105
3.4.2.The effect of IL
The different hydrophobic ionic liquid such as,
[OMIM] [PF6], [BMIM][PF6] and [EMIM][PF6]
was used for collecting and separation ligand/Cd
from water samples (Fig. 8). So, the effect of ILs on
the cadmium extraction was evaluated within the
IL range (0.1-0.5 g) by standard cadmium solution
(1-36 μg L-1). Due to results, the high recoveries
were achieved by 0.17 g of [OMIM] [PF6] (98.9%).
Therefore, 0.2 g of [OMIM] [PF6] was used as
optimum IL for Cd extraction by MBBOTSC
ligand.
3.4.3.Optimization of MBBOTSC ligand
The effect of MBBOTSC for cadmium extraction
must be evaluated. MBBOTSC is one of the important
factor for cadmium extraction which should be
optimized by the USA-D-ILLME procedure. First,
0.015 × 10−4 0.35 × 10−4 mol L−6 of MBBOTSC
ligand was examined for cadmium extraction in
the water and standard samples. Due to results, the
recovery of extraction increased for 0.065 × 10−4
0.35 × 10−4 mol L−6 of MBBOTSC ligand
(Fig. 9). So, 0.07 × 10−4 mol L−1 of MBBOTSC
ligand in 50 mL of water sample was selected as
optimum amount of ligand for cadmium extraction.
3.4.4.Effect of back-extraction eluents
The effect of back-extraction eluents for cadmium
extraction in water samples were studied by
MBBOTSC ligand. At acidic pH (pH<4), the
covalent bond between the cadmium ions and
sulfur/nitrogen groups (complexation) was broken
and cadmium ions released into eluents. For this
purpose, the different acid solutions (HCl, HNO3,
H2CO3, H2SO4) were prepared and used for back-
extraction cadmium ions fron ligand/IL in water
and wastewater samples. In-addition, the eluent
concentrations and volumes between 0.1-1.0
mol L-1 and 0.1-2.0 mL) was studied. The results
showed, the high extraction for cadmium was
achieved by 0.5 mL of nitric acid (0.5 M) (Fig. 10).
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Fig. 8. The effect of amount of IL on cadmium extraction based on MBBOTSC ligand
by the USA-D-ILLME procedure
Fig. 9. The effect of ligand on cadmium extraction by the USA-D-ILLME procedure
20 50 80 100 150 200 250 300
101
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Fig. 8. The effect of amount of IL on cadmium extraction based on MBBOTSC ligand
by the USA-D-ILLME procedure
Fig. 9. The effect of ligand on cadmium extraction by the USA-D-ILLME procedure
3.4.2.The effect of IL
The different hydrophobic ionic liquid such as,
[OMIM] [PF6], [BMIM][PF6] and [EMIM][PF6]
was used for collecting and separation ligand/Cd
from water samples (Fig. 8). So, the effect of ILs on
the cadmium extraction was evaluated within the
IL range (0.1-0.5 g) by standard cadmium solution
(1-36 μg L-1). Due to results, the high recoveries
were achieved by 0.17 g of [OMIM] [PF6] (98.9%).
Therefore, 0.2 g of [OMIM] [PF6] was used as
optimum IL for Cd extraction by MBBOTSC
ligand.
3.4.3.Optimization of MBBOTSC ligand
The effect of MBBOTSC for cadmium
extraction must be evaluated. MBBOTSC
is one of the important factor for cadmium
extraction which should be optimized by the
USA-D-ILLME procedure. First, 0.015 × 10−4
0.35 × 10−4 mol L−6 of MBBOTSC ligand
was examined for cadmium extraction in the
water and standard samples. Due to results, the
recovery of extraction increased for 0.065 × 10−4
0.35 × 10−4 mol L−6 of MBBOTSC ligand
(Fig. 9). So, 0.07 × 10−4 mol L−1 of MBBOTSC
ligand in 50 mL of water sample was selected
as optimum amount of ligand for cadmium
extraction.
3.4.4.Effect of back-extraction eluents
The effect of back-extraction eluents for
cadmium extraction in water samples were
studied by MBBOTSC ligand. At acidic pH
(pH<4), the covalent bond between the cadmium
ions and sulfur/nitrogen groups (complexation)
was broken and cadmium ions released into
eluents. For this purpose, the different acid
solutions (HCl, HNO3, H2CO3, H2SO4) were
prepared and used for back-extraction cadmium
ions fron ligand/IL in water and wastewater
samples. In-addition, the eluent concentrations
and volumes between 0.1-1.0 mol L-1 and 0.1-
2.0 mL) was studied. The results showed, the
high extraction for cadmium was achieved by
0.5 mL of nitric acid (0.5 M) (Fig. 10).
???? AbdolrezaHassanzadeh et al
Fig. 10. The effect of eluents on cadmium extraction based on MBBOTSC ligand
by the USA-D-ILLME procedure
Synthesis of MBBOTSC ligand for cadmium extraction by IL Abdolreza Hassanzadeh et al
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Fig. 8. The effect of amount of IL on cadmium extraction based on MBBOTSC ligand
by the USA-D-ILLME procedure
Fig. 9. The effect of ligand on cadmium extraction by the USA-D-ILLME procedure
1.5 2.5 4 5 66.5 7 9 20
0.2 0.4
Acid eluents (mol L -1)
0.6 0.8 1 1.2
102
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Table 2. The validation of results for cadmium extraction based on the MBBOTSC ligand in water samples by
spiking standard solution ( μg L-1).
Samples Added USA-D-ILLME Recovery (%)
Drinking Water ----- 0.45 ± 0.02 -----
0.5 0.94 ± 0.05 98.1
1.0 1.47 ± 0.07 102
Well water ----- 5.14 ± 0.19 -----
5.0 9.95± 0.44 96.2
10 15.25± 0.62 101.1
Wastewater ----- 9.85 ± 0.46
5 14.76 ± 0.67 98.2
10 19.78 ± 0.84 99.3
Wastewater ----- 12.58 ± 0.57
10 23.01 ± 1.14 104.3
20 32.31 ± 1.52 98.6
Mean of three determinations ± ccondence interval (P= 0.95, n=5)
Wastewater prepared from petrochemical industry in Arak and well water from south ofTehran (Share-Ray)
3.4.5.Effect of sample volume
The effect of sample volume for cadmium extraction
in water samples was evaluated between 5 - 100
mL with cadmium concentration (1-36 μg L-1) by
AT-F-AAS. As result, the high recovery occurred
less than 60 mL of water samples at pH 6.5. So,
50 mL was selected as optimum sample volume
for cadmium extraction based on the MBBOTSC
ligand by the USA-D-ILLME procedure.
Validation of methodology
The cadmium ions (Cd2+) was separated and
determined in water and standard samples by
the USA-D-ILLME procedure. The cadmium
ions were successfully extracted based on
MBBOTSC ligand in water samples with high
recovery. Moreover, the accuracy of cadmium
analysis must be validated by advanced analytical
techniques and spiking samples. In this study,
the results of USA-D-ILLME procedure was
validated by spiking the standard cadmium
solution in water samples (Table 2). Also, the
data analysis of cadmium in this procedure
can be validated by ET-AAS (Table 3). The
results demonstrated the accurate extraction
and high recovery for cadmium ions in water
and wastewater samples. The spiked samples
showed satisfactory results for extraction and
separation of cadmium based on the MBBOTSC
ligand in water samples by the USA-D-ILLME
procedure.
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-105
3.4.5.Effect of sample volume
The effect of sample volume for cadmium extraction
in water samples was evaluated between 5 - 100
mL with cadmium concentration (1-36 μg L-1) by
AT-F-AAS. As result, the high recovery occurred
less than 60 mL of water samples at pH 6.5. So,
50 mL was selected as optimum sample volume
for cadmium extraction based on the MBBOTSC
ligand by the USA-D-ILLME procedure.
3.5. Validation of methodology
The cadmium ions (Cd2+) was separated and
determined in water and standard samples by the
USA-D-ILLME procedure. The cadmium ions
were successfully extracted based on MBBOTSC
ligand in water samples with high recovery.
Moreover, the accuracy of cadmium analysis must
be validated by advanced analytical techniques
and spiking samples. In this study, the results
of USA-D-ILLME procedure was validated by
spiking the standard cadmium solution in water
samples (Table 2). Also, the data analysis of
cadmium in this procedure can be validated by
ET-AAS (Table 3). The results demonstrated
the accurate extraction and high recovery for
cadmium ions in water and wastewater samples.
The spiked samples showed satisfactory results
for extraction and separation of cadmium based
on the MBBOTSC ligand in water samples by the
USA-D-ILLME procedure.
4. Conclusions
An analytical method for extraction and
determination of cadmium in water samples was
carried out by synthesis of meta-(4-bromobenzyloxy)
benzaldehyde thiosemicarbazone (MBBOTSC)
as a novel ligand at pH 6.5. The complexation
between cadmium and ligand was achieved with
the MBBOTSC ligand and cadmium extracted by
the USA-D-ILLME procedure. By the proposed
procedure, the simple and fast extraction, as well
as the efcient separation for cadmium ions was
obtained at optimized conditions. Results showed
the LOD, the working range and RSD ranges were
obtained at 0.3 μg L-1, 1-75 μg L-1 and 1.12%-
2.54%, respectively. Due to results, the separation
cadmium in water samples was simply achieved by
the IL phase before determined by AT-F-AAS.
103
Anal. Methods Environ. Chem. J. 4 (4) (2021) 92-106
Table 2. The validation of results for cadmium extraction based on the MBBOTSC ligand in water samples by
spiking standard solution ( μg L-1).
Samples Added USA-D-ILLME Recovery (%)
Drinking Water ----- 0.45 ± 0.02 -----
0.5 0.94 ± 0.05 98.1
1.0 1.47 ± 0.07 102
Well water ----- 5.14 ± 0.19 -----
5.0 9.95± 0.44 96.2
10 15.25± 0.62 101.1
Wastewater ----- 9.85 ± 0.46
5 14.76 ± 0.67 98.2
10 19.78 ± 0.84 99.3
Wastewater ----- 12.58 ± 0.57
10 23.01 ± 1.14 104.3
20 32.31 ± 1.52 98.6
Mean of three determinations ± ccondence interval (P= 0.95, n=5)
Wastewater prepared from petrochemical industry in Arak and well water from south ofTehran (Share-Ray)
3.4.5.Effect of sample volume
The effect of sample volume for cadmium extraction
in water samples was evaluated between 5 - 100
mL with cadmium concentration (1-36 μg L-1) by
AT-F-AAS. As result, the high recovery occurred
less than 60 mL of water samples at pH 6.5. So,
50 mL was selected as optimum sample volume
for cadmium extraction based on the MBBOTSC
ligand by the USA-D-ILLME procedure.
Validation of methodology
The cadmium ions (Cd2+) was separated and
determined in water and standard samples by
the USA-D-ILLME procedure. The cadmium
ions were successfully extracted based on
MBBOTSC ligand in water samples with high
recovery. Moreover, the accuracy of cadmium
analysis must be validated by advanced analytical
techniques and spiking samples. In this study,
the results of USA-D-ILLME procedure was
validated by spiking the standard cadmium
solution in water samples (Table 2). Also, the
data analysis of cadmium in this procedure
can be validated by ET-AAS (Table 3). The
results demonstrated the accurate extraction
and high recovery for cadmium ions in water
and wastewater samples. The spiked samples
showed satisfactory results for extraction and
separation of cadmium based on the MBBOTSC
ligand in water samples by the USA-D-ILLME
procedure.
???? AbdolrezaHassanzadeh et al
4. Conclusions
An analytical method for extraction
and determination of cadmium in water
samples was carried out by synthesis of
meta-(4-bromobenzyloxy) benzaldehyde
thiosemicarbazone (MBBOTSC) as a novel
ligand at pH 6.5. The complexation between
cadmium and ligand was achieved with the
MBBOTSC ligand and cadmium extracted by
the USA-D-ILLME procedure. By the proposed
procedure, the simple and fast extraction, as
well as the efficient separation for cadmium
ions was obtained at optimized conditions.
Results showed the LOD, the working range
and RSD ranges were obtained at 0.3 μg L-1,
1-75 μg L-1 and 1.12%- 2.54%, respectively.
Due to results, the separation cadmium in water
samples was simply achieved by the IL phase
before determined by AT-F-AAS.
5. Acknowledgments
We thank the Department of Medicinal
Chemistry, Faculty of Pharmacy, Kerman
University of Medical Sciences, Kerman, and
Environmental Engineering, Faculty of Natural
Resources, Islamic Azad University, Bandar
Abbas Branch for support of this work.
6. References
1. L.N. Suvarapu, A.R. Somala, J.R.
Koduru, S.O.k. Baek, V.R. Ammireddy,
A Critical Review on Analytical and
Biological Applications of Thio- and
Phenylthiosemicarbazones, Asian. J. Chem,
24 (2012) 1889-1898.
2. S.A. Hosseini-Yazdi, S. Hosseinpour, A.A.
Khandar, W.S. Kassel, N.A. Piro, Copper
(II) and nickel (II) complexes with two new
bis(thiosemicarbazone) ligands: Synthesis,
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Genel, S. Birteksöz, G. Ötük, B. Ülküseven,
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Table 3. The validation of methogology for cadmium extraction and determination in water by spiking samples and
comparing to the ET-AAS analyzer
Samples Added
( μg L-1)
ET-AAS
( μg L-1)
USA-D-ILLME
( μg L-1)
Recovery (%)
ET-AAS
Recovery (%)
USA-D-ILLME
Drinking Water ----- 0.73 ± 0.03 0.69 ± 0.02 ----- -----
0.5 1.21 ± 0.05 1.22 ± 0.06 96.0 106
Well water ----- 3.76 ± 0.16 3.82 ± 0.18 ----- -----
3.0 6.72 ± 0.29 6.77± 0.32 98.6 98.3
Wastewater ----- 14.02 ± 0.71 13.87 ± 0.64
15 28.56 ± 1.28 29.03 ± 1.42 96.9 101.1
Wastewater ----- 16.32 ± 0.78 16.15 ± 0.81
20 36.25 ± 1.68 35. 58 ± 1.74 99.7 97.2
Mean of three determinations ± ccondence interval (P= 0.95, n=5)
Wastewater prepared from petrochemical industry in Arak and well water from south ofTehran (Share-Ray)
Synthesis of MBBOTSC ligand for cadmium extraction by IL Abdolreza Hassanzadeh et al
5. Acknowledgments
We thank the Department of Medicinal Chemistry,
Faculty of Pharmacy, Kerman University of Medical
Sciences, Kerman, and Environmental Engineering,
Faculty of Natural Resources, Islamic Azad University,
Bandar Abbas Branch for support of this work.
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