Synthesis and Catalytic Application of Bimetallic and Trimetallic Magnetic Nanoalloys for the Preparation of Bis(indolyl)methanes

Article abstract of DOI:10.1134/S1070428020100255

Abstract: Some bimetallic and trimetallic magnetic nanoalloys based on cobalt, copper,and silver have been synthesized and used as and green catalysts for thepreparation of bis(indolyl)methanes through electrophilic substitution reactionof indole with car

Full text of DOI:10.1134/S1070428020100255

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 10, pp. 1823–1831. © Pleiades Publishing, Ltd., 2020.
Synthesis and Catalytic Application of Bimetallic and Trimetallic
Magnetic Nanoalloys for the Preparation of Bis(indolyl)methanes
K. P. Boroujenia,*, M. Shahrokha, K. Kiania, A. Farokhniaa, R. Kazemia, and F. Kheirib
a Department of Chemistry, Shahrekord University, Shahrekord, 88186-34141 Iran
b Department of Physics, Shahrekord Branch, Islamic Azad University, Shahrekord, 88137-33395 Iran
*e-mail: parvanak-ka@sku.ac.ir
Received June 9, 2020; revised June 21, 2020; accepted June 26, 2020
Abstract—Some bimetallic and trimetallic magnetic nanoalloys based on cobalt, copper, and silver have been
synthesized and used as and green catalysts for the preparation of bis(indolyl)methanes through electrophilic
substitution reaction of indole with carbonyl compounds. The obtained nanoalloys retained their catalytic
activity after several reaction cycles. Rietveld analysis of the X-ray powder diffraction patterns revealed the
expected Co11.05Cu20.08Ag68.87 ratio in the Co–Cu–Ag nanoalloy.
Keywords: magnetic nanoalloys, bis(indolyl)methanes, catalysis, aldehyde
DOI: 10.1134/S1070428020100255
Nowadays nanoalloys are the most attractive sub-
jects of chemical research because of their remarkable
properties [1, 2] which can be very unique and com-
pletely different from those of their components [3, 4].
Nanoalloys have a high surface-to-volume ratio and
exhibit a quantum confinement effect, so they can
provide a broad spectrum of magnetic, electrical,
thermal, and chemical properties with wide applica-
tions in catalysis, electrochemical sensing and bio-
sensing, and medicinal chemistry [5–7]. Among these,
bimetallic alloy nanoparticles of Co, Cu, or Ag have
been well-established as catalysts or reagents in various
chemical transformations such as ethylene epoxidation
[8], electrocatalytic reduction of benzyl chloride [9],
oxygen reduction reactions [10], oxidation of formal-
dehyde [11], synthesis of vertically aligned carbon
nanofibers [12], methane decomposition [13], hydro-
lytic dehydrogenation of ammonia-borane [14], hydro-
gen evolution reactions [15], giant magnetoresistance
(GMR) in granular materials [16], thermal decom-
position of ammonium perchlorate [17], as antibacterial
agents [18], and in the preparation of 1,8-dioxoocta-
hydroxanthenes [19] and biscoumarins [20] along
with anti-bacterial, anti-oxidant, and DNA cleavage
properties.
1,1,3-tris(1H-indol-3-yl)butane (II) [22], 2,5-bis(1H-
indol-3-ylmethyl)pyrazine (III) [23], and tryptamine
isovalerate (IV) [23] have been isolated from micro-
organisms. Among various indole derivatives, bis(in-
dolyl)methanes (BIMs) in which two indolyl moieties
are connected to each other by a carbon atom are
known as effective biologically active molecules used
as analgesic [24], antifungal [25, 26], and anti-inflam-
matory agents [27]. Anti-cancer effect of 1,1,3-tri(1H-
indol-3-yl)cyclohexane (V) in various lung cancer cells
was investigated [28]. Complex VI based on BIMs
containing radioactive metal ions (Gd3+) [29] has been
used as a contrast agent for radioimaging and visualiza-
tion of various tissues and organs. Also, chromogenic
3,3-bisindolyl-4-azaphthalides (VII) [30, 31] have
been employed as color formers in pressure-sensitive
or heat-sensitive recording materials. The most impor-
tant methods for the synthesis of BIMs include electro-
philic substitution reactions of indole with carbonyl
compounds catalyzed by numerous Lewis and Brönsted
acid catalysts such as LiClO4 [32], I2 [33], sulfamic
acid [34], HBF4–SiO2 [35], poly(ethylene glycol)–
sulfonic acid (PEG–SO3H) [36], polystyrene–AlCl3
[37], SiO2–AlCl3 [38], Nafion–H® [39], [DABCO–H]·
[HSO4] [40], nano n-propylsulfonated γ-Fe2O3 [41],
Sc(OTf)3 [42], CaO [43], graphene oxide [44],
4-(3-methylimidazolium)butane sulfonate (MBS) [45],
hyper-cross-linked polyaromatic spheres (HCP@
CH2Br) [46], itaconic acid [47], borophosphate glasses
Indole derivatives are common secondary metab-
olites from plants, marine natural sources, microorgan-
isms, and other sources [21]. For example, 3,3-bis-
(1H-indol-3-yl)butane-2-one (I, Scheme 1) [22],
1823

BOROUJENI et al.
1824
Scheme 1.
NH
R1
R2
N
HN
Me
NH
N
HN
NH
R1 = H, acyl; R2 = H, Me
HN
NH
I
II
III
O
N
NH
H
N
O
Me
N
O
Me
N
HN
Y1
Z1
Z2
Y2
Y1 = H, Alk; Y2 = Alk
Z1, Z2 = H, Alk, Ph
HN
NH
IV
V
VII
NH
O
O
COOH
HN
HN
Ph
N
H
N
N
O
HOC(O)
HN
O
N
NH
COOH
COOH
N
COOH
HOC(O)
HOC(O)
N
N
COOH
Bis-Gd3+ complex, Na salt (VI)
[48], BF3–grafted Fe3O4@sucrose nanoparticles [49],
and multiwalled carbon nanotubes (MWCNT) grafted
with sulfonated polyacrylamide [50]. However, many
of the reported catalysts suffer from some disadvan-
tages like difficult recovery and recycling, strongly
acidic conditions, tedious work-up, the use of toxic
solvents, and formation of by-products. Therefore,
extensive research is still underway to find suitable
catalysts that can overcome the above drawbacks,
particularly from the viewpoint of green chemistry.
species or there is some limitation to combine the
active metals [57, 58]. In the previous studies we
introduced a practical reduction method for the pre-
paration of nanoalloys in aqueous solution using hydra-
zine as reducing agent [59–61]. This method proved to
be the best route to control the composition, size, and
shape of multimetallic nanoparticles. Depending on the
oxidizing agent, pH, and temperature, hydrazine reacts
in different ways. If the two metals in a complex have
different redox potentials, they form a core–shell struc-
ture, otherwise a bimetallic alloy is obtained [62, 63].
Various synthetic techniques have been reported for
preparing nanoalloys such as laser ablation, polyol
synthesis, codeposition, solvothermal and colloidal
syntheses, microwave irradiation, and chemical vapor
deposition [51–56]. Although these methods are valu-
able, some drawbacks still remain. In particular, there
is no guarantee for the formation of the exact desired
Considering the above discussion, the Co–Cu and
Co–Ag bimetallic nanoalloys were synthesized from
the corresponding [Cu(C2O4)2]3[Co(NH3)6]2 and
[Co(NH3)6]Cl3 complexes and AgNO3 in hydrazine
[19, 60]. The reduction of Co–Cu nanoalloy with
AgNO3 and excess hydrazine led to the formation of
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SYNTHESIS AND CATALYTIC APPLICATION OF BIMETALLIC ...
1825
Scheme 2.
[Cu(C2O4)2]3[Co(NH3)6]2 + 3N2H4 + 12NaOH
Co2Cu3 + 3N2 + 12NH3 + 6Na2C2O4 + 12H2O
[Co(NH3)6]Cl3 + AgNO3 + N2H4 + 4NaOH
CoAg + N2 + 6NH3 + 3NaCl + NaNO3 + 4H2O
[Cu(C2O4)2]3[Co(NH3)6]2 + 4AgNO3 + 4N2H4 + 16NaOH
Co2Cu3Ag4 + 4N2 + 12NH3 + 6Na2C2O4 + 4NaNO3 + 6H2O
Co–Cu–Ag nanoalloy. The reactions were carried out
in aqueous ethanol as shown in Scheme 2.
Counts
Co
Ag
Cu
The crystal structures of Co–Cu and Co–Ag NPs
have been studied by X-ray powder diffraction. It was
found that Co and Cu were reduced to form face-
centered cubic (fcc) phase [60]. The X-ray powder
pattern for Co–Ag nanoalloy showed that it was
composed of fcc and hcp (hexagonal close-packed) Co
phases and fcc Ag phase [19]. The diffraction peaks for
Co–Cu–Ag nanoalloy showed that it is in fcc phase and
that it can be considered as Co/Cu/Ag NPs (Fig. 1).
The diffraction peaks are in good agreement with the
standard values for Cu (card no. 85-1326), Co (card
no. 01-1254), and Ag (card no. 01-1164). In most
studies of the grain size of nanocrystalline materials,
X-ray line-broadening analysis is used [62]. The
crystallite size could be estimated from the full width
at half maximum (FWHM) of the diffraction peaks.
The mean crystallite size was calculated by the
Scherrer formula [64] (Table 1).
1000
500
0
20
30
40
50
60
70
80
2θ, deg
Fig. 1. X-Ray powder diffraction pattern of Co–Cu–Ag NPs.
To estimate the relative phase abundances, struc-
tural changes, and microstructure parameters of indi-
vidual phases, the XRD patterns were analyzed by the
Rietveld method [65] using FullProf software package.
The results of the Rietveld refinements are presented in
Fig. 2. The experimental data (dotted lines) were fitted
well with the refined simulated patterns (vertical
hashed lines). The difference curve of the observed
powder pattern intensities and the calculated ones
was displayed near the bottom of the graph with a zero
line. Clearly, there is good agreement between the
observed patterns and all the fittings. The results of the
Rietveld refinements were presented in the expected
Co11.05Cu20.08Ag68.87 ratio in Co–Cu–Ag NPs.
9
17
25
33
41
49
57
65
73
2θ, deg
Fig. 2. Observed (dotted lines) and calculated (vertical
hashed lines) diffraction patterns for Co–Cu–Ag NPs. The
difference between the observed and calculated patterns is
plotted at the bottom of the diagram.
Transmission, %
100
80
60
40
20
0
The FT–IR spectrum of Co–Cu–Ag NPs is shown
in Fig 3. The chemical reactions resulted in complete
decomposition of primary complexes, and absorption
bands related to the ligand groups disappeared. There-
fore, the FT–IR spectrum has no absorption bands in
the medium IR region, and only weak absorption bands
due to adsorbed water in the NPs are observed.
4000
3000
2000
1000
Magnetic property measurements were also carried
out using vibrating sample magnetometry (VSM).
The ferromagnetic behavior of Co–Cu–Ag NPs at
ν, cm–1
Fig. 3. FT-IR spectrum of Co–Cu–Ag NPs.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 10 2020

BOROUJENI et al.
1826
Table 1. Crystallite size in Co–Cu, Co–Ag, and Co–Cu–Ag
nanoalloys
NPs and that the Ms value of Co NPs is lower than that
of bulk Co (about 160 emu/g at 300 K) [66]. Also, the
magnetic properties of NPs showed decrease of the Ms
values with increase in the Cu and Ag concentrations,
which can be related to the presence of dissolved Co in
the Cu and Ag matrix.
Nanoalloy
Crystallite size, nm
hkl
Co–Cu
29
(111)
(111)
(111)
Co–Ag
35.69
28.49
Co–Cu–Ag
The physical morphologies of the NPs were
examined using scanning electron microscopy (SEM).
Morphology of the prepared NPs was found to be
dependent on the initial complex salts. The SEM
images of Co–Cu NPs showed nearly monodisperse
spherical and uniform particles [60], whereas Co–Ag
NPs were agglomerated spherical particles [19]. The
particle size distribution graphs for Co–Cu and Co–Ag
samples were obtained from field emission (FE) SEM
analysis, according to which the average diameter of
a maximum number of particles was found to be in the
range of 15 and 40–50 nm, respectively. The SEM
images of Co–Cu–Ag NPs revealed that uniform mor-
phology in Co–Cu in the presence of Ag changed to
the agglomeration morphology containing nanosheets
(Fig. 5). The sheets in the images have an average
width of 20 nm with an average length of 80 nm.
room temperature is illustrated by Fig. 4; it is similar to
the behavior of Co–Cu and Co–Ag NPs [19, 60]. The
saturation magnetization values (Ms) of Co–Cu,
Co–Ag, and Co–Cu–Ag NPs at 300 K are 38.77, 6, and
4.08 emu/g, respectively. This proves that the Ms value
of trimetallic NPs is less than those of the bimetallic
4.08
3.06
2.04
1.02
0.00
–1.02
–2.04
–3.06
–4.08
–5.10
The different dispersion of the metallic phases can
also be explained by considering the energy-dispersive
X-ray (EDX) data. Figure 6 shows the EDX spectrum
of Co–Cu–Ag NPs. The signals at 6.9 and 8.1 keV
correspond to Co and Cu, respectively. The signals at 7
and 7.6 keV were assigned to the Kα and Kβ transitions
for Co, respectively, and the signals at 3 and 3.2 keV, to
the Lα and Lβ transitions for Ag, respectively. Thus,
the EDX analysis also demonstrated the presence of
three metals in Co–Cu–Ag NPs and their purity.
–10000
–6000
–2000 0 2000
Applied field, Oe
6000
10000
Fig. 4. Magnetization curve of Co–Cu–Ag NPs.
1400
1200
1000
800
600
400
200
0
0
2
4
6
8
10
Energy, keV
Fig. 5. SEM image of Co–Cu–Ag NPs.
Fig. 6. EDX spectrum of Co–Cu–Ag NPs.
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SYNTHESIS AND CATALYTIC APPLICATION OF BIMETALLIC ...
1827
Table 2. Synthesis of bisindolylmethanes by reactions of aldehydes with indole in the presence of magnetic nanoalloy
catalysts
Co–Cu (0.05 g) (i) or
Co–Ag (0.05 g) (ii) or
Co–Cu–Ag (0.04 g) (iii)
R
MeCN, reflux
2
+ RCHO
N
H
HN
NH
1–11
Compd.
no.
Aldehyde (RCHO)
PhCHO
Time, min
Yield,a %
mp, °C
1
2
38 (i), 39 (ii), 38 (iii)
42 (i), 43 (ii), 41 (iii)
46 (i), 47 (ii), 44 (iii)
37 (i),38 (ii), 35 (iii)
30 (i), 33 (ii), 30 (iii)
35 (i), 36 (ii), 33 (iii)
37 (i), 39 (ii), 32 (iii)
33 (i), 36 (ii), 32 (iii)
46 (i), 50 (ii), 45 (iii)
40 (i), 42 (ii), 38 (iii)
38 (i), 40 (ii), 36 (iii)
97 (i), 96 (ii), 97 (iii)
93 (i), 92 (ii), 94 (iii)
93 (i), 92 (ii), 94 (iii)
93 (i), 92 (ii), 94 (iii)
96 (i), 95 (ii), 97 (iii)
94 (i), 94 (ii), 95 (iii)
96 (i), 95 (ii), 95 (iii)
96 (i), 95 (ii), 95 (iii)
91 (i), 91 (ii), 92 (iii)
94 (i), 93 (ii), 95 (iii)
95 (i), 95 (ii), 93 (iii)
122–125 (126–127 [34])
92–95 (95–97 [34])
4-MeC6H4CHO
4-MeOC6H4CHO
2-ClC6H4CHO
2,4-Cl2C6H3CHO
4-BrC6H4CHO
4-O2NC6H4CHO
3-O2NC6H4CHO
Me(CH2)4CHO
3
188–190 (187–189 [33])
73–76 (72–74 [33])
4
5
106–108 (109–111 [50])
114–117 (112–113 [34])
218–220 (217–219 [33])
215–219 (214–218 [50])
71–75 (70–73 [50])
6
7
8
9
10
11
Thiophene-2-carbaldehyde
Furan-2-carbaldehyde
153–157 (151–153 [33])
319–322 (322–325 [33])
a
Isolated yield. All products are known compounds and were identified by comparison of their physical and spectral data with those of
authentic samples.
In continuation of our research on the synthesis of
BIMs using heterogeneous catalysts [37, 38, 50], we
examined the catalytic activity of Co–Cu, Co–Ag, and
Co–Cu–Ag NPs in the preparation of BIMs. The
reaction between 1 mmol of 4-nitrobenzaldehyde and
2 mmol of indole was used as a model to optimize the
conditions such as temperature, solvent, and catalyst
loading. The reaction proceeded well in refluxing
acetonitrile and afforded the desired product in the
presence of 0.05 g of Co–Cu or Co–Ag NPs or 0.04 g
of Co–Cu–Ag NPs. Under the optimal conditions,
a variety of aromatic and aliphatic aldehydes contain-
ing both electron-withdrawing and electron-donating
substituents were treated with indole, and the corre-
sponding BIMs were obtained in good to excellent
yields (Table 2). The reaction conditions can be
regarded as mild, and the BIMs were exclusively
formed without any undesirable by-products that are
normally formed in the presence of strong acids.
Ketones reacted in a longer time with very low yields,
probably due to steric effects. For instance, in the reac-
tion of acetophenone (1 mmol) with indole (2 mmol)
even in the presence of excess Co–Cu–Ag NPs (e.g.,
0.1 g), the yield was significantly lower than 30% after
Scheme 3.
R
R
H
Cat
H
H
OH
R
H
OH
O
–H+
Cat
N
H
N
H
N
H
H
N
R
R
R
H
H
H+
–H+
–H2O
HN
N
HN
NH
N
H
H
A
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BOROUJENI et al.
1828
Table 3. Catalytic efficiency of Co–Cu, Co–Ag, and Co–Cu–Ag nanoalloys and other reported catalysts for the reaction of
one benzaldehyde (1 equiv) with indole (2 equiv)
Entry no.
Catalyst, solvent, temperature
LiClO4, MeCN, r.t.
Time, min
300
10
Yield,a %
90 [32]
72 [33]
30 [34]
94 [35]
95 [36]
95 [37]
96 [38]
94 [39]
91 [40]
82 [41]
92 [42]
70 [43]
92 [44]
86 [45]
96 [46]
90 [47]
94 [48]
92 [49]
97 [50]
97
1
2
I2, solvent-free, r.t.
3
Sulfamic acid, solvent-free, r.t.
HBF4-SiO2, solvent-free, r.t.
PEG–sulfonic acid, MeOH, r.t.
Polystyrene–AlCl3, MeCN, reflux
SiO2-AlCl3, solvent-free, r.t.
Nafion-H®, PEG/H2O (60/40), 80°C
[DABCO-H][HSO4], neat, 90°C
Nano-n-propylsulfonated γ-Fe2O3, solvent-free, 80°C
Sc(OTf)3, THF, plug flow, r.t.
CaO, solvent-free, 100°C
92
4
10
5
150
60
6
7
35
8
25
9
120
60
10
11
210
210
180
60
12
13
Graphene oxide, H2O, 40°C
14
MBS, neat, r.t.
15
HCP@CH2Br, neat, 60°C
60
16
Itaconic acid, H2O, 100°C
120
90
17
Borophosphate glasses, solvent-free, 70°C
Fe3O4@sucrose–OBF3H, EtOAc, 70°C
MWCNT-sulfonated polyacrylamide, MeCN, reflux
Co–Cu, MeCN, reflux
18
150
37
19
20
38
21
22
Co–Ag, MeCN, reflux
39
96
Co–Cu–Ag, MeCN, reflux
38
97
a Isolated yield.
3 h in refluxing acetonitrile. The results showed that
Co–Cu–Ag nanoalloy is more active in the preparation
of BIMs than both Co–Cu and Co–Ag nanoalloys with
respect both reaction time and catalyst amount; pre-
sumably, Co–Cu–Ag nanoalloy NPs possess a larger
number of catalytically active sites that promote the
reaction. To the best of our knowledge, the use of
magnetic nanoalloys as catalyst for the preparation of
BIMs has not been reported previously.
A probable mechanism for the synthesis of BIM
derivatives is outlined in Scheme 3. An aldehyde is
first activated by the nanoalloy as a Lewis acid.
Nucleophilic addition of an indole molecule to the ac-
tivated aldehyde, followed by loss of waster molecule,
gives intermediate A, and addition of the second indole
molecule to A yields the final product [21].
Yield, %
100
Co–Cu
98
Co–Ag
Co–Cu–Ag
96
The isolation and recovery of homogeneous cata-
lysts from the reaction mixture are generally difficult.
The use of magnetic catalysts has emerged as a viable
solution; magnetic nature enables easy and efficient
separation of these catalysts from the reaction mixture
with an external magnet. In each cycle, the catalysts
were easily recovered by magnetic separation and
reused at least seven times (Fig. 7).
94
92
90
2
3
4
5
6
7
Run no.
Fig. 7. Recyclability of Co–Cu (0.05 g), Co–Ag (0.05 g), and
Co–Cu–Ag (0.04 g) catalysts after 37, 39, and 32 min,
respectively, in the reaction of 1 mmol of 4-nitrobenzaldehyde
with 2 mmol of indole in refluxing acetonitrile.
Finally, the efficiency of Co–Cu, Co–Ag, and
Co–Cu–Ag NPs was compared with that of other cata-
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SYNTHESIS AND CATALYTIC APPLICATION OF BIMETALLIC ...
1829
lysts reported earlier for the preparation of BIMs
(Table 3). As can be seen, these NPs have good
catalytic performance in terms of easy separation,
yield, and reaction rate in comparison with many other
catalysts.
room temperature for 24 h. The Co–Ag NPs were
synthesized in a similar way using [Co(NH3)6]Cl3
complex and AgNO3 [19].
Preparation of Co–Cu–Ag NPs. The Co–Cu NPs
prepared as described above were treated with 25 mL
of a 0.01 M solution of AgNO3, excess hydrazine, and
4 M NaOH at 50–60°C. The resulting nanoparticles
were carefully washed with doubly distilled water and
acetone and dried at room temperature for 24 h.
In conclusion, Co–Cu, Co–Ag, and Co–Cu–Ag
nanoalloys were easily prepared from their basic ingre-
dients and employed as highly efficient magnetic
catalysts for the synthesis of BIM derivatives. These
catalysts can be easily separated using an external
magnet, and their catalytic activity remains after
several reaction cycles. Simple experimental and work-
up procedures, clean reaction, and high reaction rates
and yields without formation of by-products are other
obvious advantages of the proposed method.
Typical procedure for the preparation of bis-
imidazolylmethanes. A mixture of 4-nitrobenzalde-
hyde (1 mmol), indole (2 mmol), and Co–Cu (0.05 g),
Co–Ag (0.05 g), or Co–Cu–Ag (0.04 g) in acetonitrile
was refluxed with stirring. After completion of the
reaction (TLC, eluent chloroform), the catalyst was
separated by an external permanent magnet and washed
with acetonitrile. The combined filtrates were evap-
orated on a rotary evaporator, and the product was pu-
rified by recrystallization from ethanol. 3,3′-[(4-Nitro-
phenyl)methylene]di(1H-indole), mp 218–220°C
EXPERIMENTAL
All chemicals were of the highest available purity
and were used as received. Progress of the reaction and
purity of the products were monitored by GLC and
TLC (Polygram SILG/UV254 plates). Gas chromato-
graphic analyses were performed with a Shimadzu
GC-14A instrument. The IR spectra were recorded
using a Shimadzu Model 8300 FT-IR system. The
1H NMR spectra were recorded at room temperature on
a Bruker DPX400 (400 MHz) spectrometer using
CDCl3 as solvent. The melting points were measured
using a Fisher–Jones melting point apparatus. The
X-ray diffraction (XRD) patterns were recorded by
a Philips X’Pert Pro Super diffractometer (Cu Kα radia-
tion, graphite monochromator); the relative metal
phase abundances were determined using FullProf soft-
ware. Field emission scanning electron microscopy
(FESEM, Hitachi S-4160, Japan) was used to analyze
morphology of the nanoparticles. The magnetic prop-
erties of nanoalloy samples were examined with
a LakeShore vibrating sample magnetometer at room
temperature; applied magnetic field sweeping between
±10000 Oe.
1
(217–219°C [33]). H NMR spectrum, δ, ppm: 5.93 s
(1H, Harom), 6.61 d (2H, Harom), 6.93–6.97 m (3H,
H
arom), 7.18–7.63 m (7H, Harom), 7.92 br.s (2H, NH),
8.02–8.15 m (2H, Harom).
ACKNOWLEDGMENTS
The authors are thankful to the Research Council of
Shahrekord University for partial support of this study.
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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