In situ supported of silver nanoparticles on Thymbra spicata extract coated magnetic nanoparticles under the ultrasonic condition: Its catalytic activity in the synthesis of Propargylamines and their anti-human colorectal properties in the in vitro condit

Article abstract of DOI:10.1016/j.molliq.2021.116451

This work describes an eco-friendly approach for in situ immobilization of Ag nanoparticles on the surface of Fe₃O₄ nanoparticles, with the help of Thymbra spicata extract and ultrasound irradiations, without using any toxic reducing

Full text of DOI:10.1016/j.molliq.2021.116451

Journal of Molecular Liquids 338 (2021) 116451
Contents lists available at ScienceDirect
Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
In situ supported of silver nanoparticles on Thymbra spicata extract
coated magnetic nanoparticles under the ultrasonic condition: Its
catalytic activity in the synthesis of Propargylamines and their anti-
human colorectal properties in the in vitro condition
a
b
a
c
d
Tian Tang , Qingjie Xia , Junliang Guo , Arunachalam Chinnathambi , Sara T. Alrashood ,
c
e,
⇑
Sulaiman Ali Alharbi , Jie Zhang
a
Center for Reproductive Medicine, Department of Gynecology and Obstetrics, West China Second University Hospital, Key Laboratory of Birth Defects and Related Diseases of Women
and Children, Ministry of Education, Sichuan University, Chengdu City 610041, Sichuan, China
West China Laboratory of Molecular Genetics, Sichuan University, Chengdu 610041, PR China
Department of Botany and Microbiology, College of Science, King Saud University, PO Box -2455, Riyadh 11451, Saudi Arabia
Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia
b
c
d
e
Key Laboratory of Transplant Engineering and Immunology, NHFPC, Regenerative Medicine Research Center, West China Hospital, Sichuan University, Chengdu, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
This work describes an eco-friendly approach for in situ immobilization of Ag nanoparticles on the surface
Received 3 August 2020
Revised 31 March 2021
Accepted 6 May 2021
Available online 11 May 2021
of Fe
using any toxic reducing and capping agents. The combination of Fe
nanostructure (Fe @T. spicata/Ag NPs) represents a promising strategy for targeted biomedical applica-
3
O
4
nanoparticles, with the help of Thymbra spicata extract and ultrasound irradiations, without
3 4
O
NPs and Ag NPs in one hybrid
3 4
O
tions. The structure, morphology, and physicochemical properties were characterized by various analyt-
ical techniques such as fourier transformed infrared spectroscopy (FT-IR), field emission scanning
electron microscopy (FESEM), transmission electron microscopy (TEM), energy dispersive X-ray spec-
troscopy (EDS), X-ray diffraction (XRD), inductively coupled plasma (ICP) and vibrating sample magne-
tometer (VSM). Towards the chemical applications of the material, we headed the multicomponent
synthesis of diverse propargylamines by A3 coupling in water, which ended up with excellent yields.
Due to strong paramagnetism, the catalyst was easily isolable and reused in 8 cycles without any leaching
and considerable change in reactivity. DPPH test revealed similar antioxidant potentials for hybrid nanos-
tructure and butylated hydroxytoluene. The hybrid nanostructure inhibited half of the DPPH molecules in
the concentration of 139 µg/mL. To survey the anti-human colorectal cancer activities of the hybrid
nanostructure, MTT assay was used on common human colorectal cancer cell lines. The hybrid nanostruc-
ture had very low cell viability and anti-human colorectal cancer effects dose-dependently against
Ramos.2G6.4C10, HCT-8 [HRT-18], and HCT 116 cell lines. The IC50 values of the hybrid nanostructure
were 289, 311, and 174 µg/mL against Ramos.2G6.4C10, HCT-8 [HRT-18], and HCT 116 cell lines, respec-
tively. It is thought that the hybrid nanostructure obtained can be used as an anticancer drug for the diag-
nosis of colorectal cancer in humans after acceptance of the above findings in clinical study trials.
Ó 2021 Published by Elsevier B.V.
Keywords:
Ultrasound
Magnetic
Silver
Propargylamines
Human colorectal cancer
Chemotherapeutic drug
1
. Introduction
Nanobiotechnology is a combination of nanotechnology and
come to the fore as a science that has led to reform changes in
medicines. Nanomaterials, which are the subject of our study, have
unique competencies different from their macro-scale counter-
parts due to their low volume/surface ratio and many advanced
and new physiochemical properties such as color, solubility,
strength, prevalence, toxicity, magnetic, optical, thermodynamics
biotechnology and has a remarkable role in the development and
application of many useful tools and technologies in life science-
related research [1,2]. In the past decade, nanobiotechnology has
[
1-3].
In recent years, biological methods that non-toxic, cost-
effective, and environmentally friendly have become the focus of
⇑
Corresponding author.
E-mail address: zjie2016@sina.com (J. Zhang).
https://doi.org/10.1016/j.molliq.2021.116451
167-7322/Ó 2021 Published by Elsevier B.V.
0

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
interest compared to physicochemical nanoparticle synthesis
methods [2,3]. Various pathways have been developed for the bio-
genic or biological formulation of nanomaterials from the salts of
different metal ions. The synthesis of nanoparticles under purely
such as sensing, adsorption, degradation of dyes and contaminants,
disposal of heavy and toxic metals, drug delivery, biomedical appli-
cations and catalysis [15-21]. Among the different noble metal
nanoparticles, Ag NPs are relatively cheaper as compared to Au,
Pd and Pt. Based on their distinct characteristics the Ag NPs indi-
vidually find multilayered applications in a different arena like
health, medicine, animal husbandry, agriculture, household, pack-
aging, optics, electronics and catalysis [5,16]. Nevertheless, due to
ultrafine size and strong electrostatic attraction, frequently the NPs
are found to undergo self-aggregation which reduces their effi-
ciency considerably. The biomolecular encapsulated nanocompos-
ite creates a polar environment at the surface that shelters the
incoming noble ions. They sometimes get reduced in situ by the
electron rich oxidisable groups or need some external reductant
to generate metallic NPs. In addition, the organic groups act as pro-
tective capping agents. This in turn, prevents the surface NPs from
associating and gets stabilized [22-24].
’
green’ principles can be achieved using an environmentally com-
patible solvent system with environmentally friendly stabilizing
and reducing factors [2]. The basic principle in the biogenesis of
nanoparticles is reducing metal ions of several biomolecules found
in organisms. In addition to reducing the environmental impact of
biological synthesis, it enables the production of large quantities of
nanoparticles, which are well defined in size and morphology,
independent of contamination. Microorganisms, marine algae,
plant extracts, plant tissue, fruits, and all plants are administrated
to formulate nanomaterials [3]. Reducing metal ions using biolog-
ical materials has been a known method since the 1900s. Due to
the poor understanding of the mechanisms of the reducing agents,
it has increased interest in the past 30 years [2]. Recently, scientists
have revealed that biological materials-metallic nanoparticles have
excellent anti-cancer properties. Metallic nanoparticles have
achieved notable consideration in the field of medicine. Some stud-
ies conducted today have shown that some nanoparticles have
therapeutic properties and it is an excellent alternative to physic-
ochemically different metal-supported nanoparticles, antibacterial,
and especially anticancer drugs [1-3].
3 4
The unique coalescence of Ag NPs and Fe O has found a broad
range of utility in biological targeting, biological separation, high
density magnetic recording and catalysis. There have been several
in vitro and in vivo experimental studies on its chemotherapeutic
activities as well as clinical trials [25-28]. Being encouraged by
all these results and as a part of our endeavor towards the develop-
ment of sustainable protocols in catalytic methodology [13,29-34],
we wish to report the synthesis, characterizations and applications
of novel Ag NPs decorated Thymbra spicata extract modified-
A major wing of the current heterogeneous catalysis is being
oriented around using novel hybrid biomolecular functionalized
magnetic nanomaterials. These featured materials are advanta-
geous in terms of biocompatibility, improvised architecture, site
dependant physicochemical properties, exceptional thermal and
mechanical stability, improved catalytic activity due to a large
number of exposed catalytic sites and facile isolation and reusabil-
3 4
magnetite nanocomposite (Fe O @T. spicata/Ag NPs). The biomole-
cules of extract afford additional stability to the MNPs from
unwanted oxidation and corrosion [35-37]. Thereby, we explored
our catalyst in the competent one-pot multicomponent synthesis
3
of Propargylamines by well-known A -coupling of aldehydes, ami-
ity [4-9]. In this connection Fe
3
O
4
nanoparticles have been evolved
nes and alkynes. Propargylamines are important structural scaf-
folds in organic synthesis, being used as precursors of several
as a potential core to be modified with suitable biomolecules. In
addition to their facile subjectibility towards functionalization,
they involve high magnetic permeability, large specific surface
area, low cost and easy synthetic method [4,10-14]. Moreover,
impregnation of noble metals over Fe O biocomposites introduces
3 4
some synergistic properties that augments their potential applica-
tions. They have been wonderfully implemented in diverse fields
biologically active compounds [38-42]. In the current protocol, Fe
3
-
O
4
@T. spicata/Ag NPs nanocomposite catalyzes the reaction effi-
ciently in aqueous medium under heating conditions to afford
the corresponding product in good to excellent yields (Scheme 1).
Due to the easy recoverability of the catalyst, it was recycled in 8
successive runs over this reaction. Besides catalysis, we extended
Scheme 1. Schematic fabrication of Fe
3
O
4
@T. spicata/Ag NPs mediated by Thymbra spicata extract under ultrasonic irradiations and its application for the synthesis of
Propargylamines.
2

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
the application of our material in the bio-assay against colorectal
3.73 (br, 4H), 2.62 (br, 4H). 13C NMR (CDCl
131.77, 129.71, 128.27, 128.19, 123.01, 113.56, 88.26, 85.34,
3
, 62.9 MHz): 159.22,
(
Ramos.2G6.4C10, HCT-8 [HRT-18], and HCT 116) cancer cell lines.
6
7.13, 61.44, 55.27, 49.79.
2
. Experimental
2
3 4
.5. Determination of the antioxidant activities of Fe O @T. spicata/Ag
2.1. Material
nanocomposite
Antimycotic antibiotic solution, dimethyl sulfoxide (DMSO),
To study the radical scavenging antioxidant property of our Fe
@T. spicata/Ag nanocomposite, DPPH (2,2-diphenyl-1-
picrylhydrazyl) is being used [1-3].
3
-
hydrolyzate, Ehrlich solution, decamplmaneh fetal bovine serum,
borax-sulfuric acid mixture, Dulbazolic mixture Modified Eagle
Medium (DMED), 4- (Dimethylamino) benzaldehyde, 2,2-
diphenyl-1- pikrilhydrazil (DPPH) and phosphate buffer solution
O
4
A 39.4% DPPH solution (w/V) was prepared in 1:1 aqueous
3 4
MeOH. At the same time, different samples of Fe O @T. spicata/
(
PBS) were supplied from the US Sigma-Aldrich company.
Ag nanocomposite of variable concentrations (0–1000 µg/mL) were
3 4
prepared. The DPPH solution was then added to Fe O @T. spicata/
Ag nanocomposite samples and incubated at 37 °C.
2.2. Preparation of Thymbra spicata leaf extract
After 30 min of incubation, the absorbances of the mixtures
were measured at 570 nm. MeOH (50%) and butylated hydroxy-
toluene (BHT) were considered as negative and positive controls
respectively in the study.
The antioxidant property of Fe O @T. spicata/Ag nanocomposite
3 4
was determined in terms of % inhibition and expressed as
One hundred grams of Thymbra spicata dried leaves were
ground and refluxed at 70 °C with 500 mL of sterile distilled water
for 2 h. Afterward, the mixture was cooled down to room temper-
ature. The aqueous extract of Thymbra spicata leaves was cen-
trifuged at 6500 rpm. Moreover, the supernatant was separated
o
by filtration and was kept in a refrigerator at 4 C for later
investigations.
Sample A:
Control A:
Inhibition ð%Þ ¼
ꢀ 100
2.3. Preparation of the biologically active magnetic Fe
3 4
O @T. spicata/
Ag nanocomposite
2
.6. Determination of anti-human colorectal cancer properties of
O
3 4
In the first step, magnetite nanoparticle (0.5 g) was dispersed in
00 mL water and sonicated for 20 min at 60 °C. Next, the Thymbra
Fe @T. spicata/Ag nanocomposite
1
spicata extract was added to the mixture. Afterwards, the solution
was sonicated again at this temperature for 60 min, and subse-
quently, a solution of AgNO in water was added dropwise using
3
a dropping funnel in the reaction media (0.03 g, 20 mL, the drip
rate was 1 mL/min) under sonication. After complete addition,
the reaction continued for another 60 min under ultrasonic condi-
tions. Then, the mixture was cooled to room temperature and the
In this assay, following human colorectal cancer cell lines and
the normal cell line (HUVEC) were used to study the cytotoxicity
and anticancer potentials of human colorectal over the Fe @T.
spicata/Ag nanocomposite using the common cytotoxicity experi-
ment i.e., MTT assay in vitro condition:
3 4
O
(
A) Normal cell line
3 4
magnetic nanoparticles Fe O @T. spicata/Ag as a dark solid was iso-
–
HUVEC.
lated from the solution by magnetic separation and washed several
times by DI water and ethanol. The final nanocomposite was dried
in a vacuum at 40 °C. The concentration of silver was 0.041 mmol/
g, which was determined by ICP-OES.
(
B) Colorectal cancer cell lines
–
–
–
Ramos.2G6.4C10
HCT-8 [HRT-18]
HCT 116
2
.4. General procedure for the synthesis of Propargylamines catalyzed
For culturing the above cells, different materials including peni-
cillin, streptomycin, and Dulbecco’s modified Eagle’s medium
by Fe @T. spicata/Ag nanocomposite
3 4
O
(
DMEM) were used [2,3]. In this test, the distribution of cells was
A mixture of aldehyde (1 mmol), amine (1 mmol), phenyl acet-
ylene (1.2 mmol) and Fe @T. spicata/Ag nanocomposite (20 mg,
.1 mol%) was heated in water (3 mL) at 80 °C for requisite times.
After completion (as monitored by TLC), the catalyst was retrieved
by a magnet for recycling. The reaction mixture was extracted with
ethyl acetate, concentrated and purified through column chro-
matography (7:3, Hexane/EtOAc).
10,000 cells/well in 96-well plates.
O
3 4
All samples were transferred to a humidified incubator contain-
0
ing 5% CO
with the different Fe O
2
at 37 °C. After 24 h incubation, all cells were treated
@T. spicata/Ag nanocomposite samples
3 4
(0–1000 µg/mL) and incubated again for 24 h. Subsequently, they
were sterilized by UV-radiation for 2 h. Then 5 mg/mL of MTT
was added to all wells and incubated again for 4 h at 37 °C.
The percentage of cell viability of samples were determined fol-
lowing the given formula after the measurement of absorbance at
570 nm.
1
13
2
.4.1. H NMR and C NMR for selected products in the Table 2:
1
(
Table 2, entry 1): H NMR (CDCl
3
, 250 MHz): d 7.65–7.62 (m,
2
2
1
H), 7.51 (m, 2H), 7.37–7.26 (m, 6H), 4.80 (s, 1H), 3.74 (br, 4H),
1
3
Sample A:
Control A:
.64 (br, 4H), CNMR (CDCl
28.21, 127.76, 122.97, 88.49, 85.03, 67.13, 62.03, 49.86.
Table 2, entry 6): 1HNMR (CDCl
, 250 MHZ): d 7.52–7.49 (m,
H), 7.34–7.16 (m, 5H), 4.75 (s, 1H), 3.73–3.71 (br, 4H), 2.63 (br,
3
, 62.9 MHz): 137.77, 131.79, 128.57,
Cell viability ð%Þ ¼
ꢀ 100
(
3
4
4
1
6
1
3
H), 2.36 (s, 3H).
31.78, 128.90, 128.50, 128.27, 128.18, 123.03, 88.23, 85.32,
7.15, 61.78, 49.86, 21.10.
3
NMR (CDCl , 62.9 MHz): 137.47, 134.78,
2.7. Qualitative measurement
The obtained results were loaded into the ‘‘SPSS-22” program
and evaluated by ‘‘one-way ANOVA”, accompanied by a ‘‘Duncan
post-hoc” check (p ꢁ 0.01).
(
Table 2, entry 7): 1H NMR (CDCl
3
, 250 MHZ): d 7.55–7.52 (m,
4
H), 7.33–7.26 (m, 3H), 6.92–68 (d, 2H), 4.74 (s, 2H), 3.82 (s, 3H),
3

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
3
. Results and discussion
3.1. Catalyst characterization data analysis
In this work, an ecofriendly approach was utilized to prepare
the Fe
The Fe
ultrasonic conditions. In the next step, the extract modified-
Fe nanocomposite is applied as a magnetic absorbent for coor-
3
O
4
@T. spicata/Ag nanocomposite, as shown in Scheme 1.
3 4
O NPs were first coated by Thymbra spicata extract under
3 4
O
dinating and reducing the silver ions and its stabilizing on the sur-
face. The Ag ions were in situ reduced to Ag NPs, in the existence of
ultrasound waves by the help of extract biomolecules. The Ag con-
ꢂ1
tent of the prepared nanocomposite was 0.041 mmol g , based on
the conducted atomic absorption spectroscopy. The structural
properties of the nanocatalyst were investigated by several analyt-
ical techniques such as FT-IR, FESEM, EDS, TEM, ICP, VSM and XRD
analysis.
In order to rationalize the stepwise synthesis of Fe
3 4
O @T. spi-
cata/Ag NPs nanocomposite, FT-IR spectra of all the corresponding
intermediates have been depicted in Fig. 1. Bare unmodified Fe
3
O
4
ꢂ1
NPs show a typical absorption at 585 and 638 cm due to FeAO
stretching (Fig. 1a). The characteristic absorption bands of Thymbra
spicata extract are represented in Fig. 1b as, 3370 (OH), 2924
(
CAH), 1619 (CO), 1400 to 2600 (C@C), 1286 (CAO), 1071 (CAOAC)
3 4
Fig. 2. FESEM image of Fe O @T. spicata/Ag NPs.
ꢂ1
and 865 cm (OAH) and represent polyols, carbonyls and the C@C
bonds of flavonoids and terpenoids [10]. Fig. 1c, representing the
FT-IR spectrum of Fe O @T. spicata/Ag NPs is literally an amalga-
3 4
mation of both individual component peaks with a slight shifting
of characteristic peaks due to strong complexation of Ag atoms
with the surface functions like OH, CHOH, CH
2
OH, C@O etc, which
is a clear sign of successful functionalization of the biomolecules
and Ag NPs over Fe
Fe-O stretching has also been moved to 568 cm which means
that the Ag chelation has an effect up to the center core [10].
3
O
4
NPs. Interestingly, the strong peak due to
ꢂ1
The detailed morphological structure, shape and size of the Fe
3
-
O
4
@T. spicata/Ag NPs nanocomposite was ascertained by SEM and
TEM studies. The globular shape nanoparticles can be observed
from SEM image having mean diameter of ꢃ 20 nm (Fig. 2). The
3 4
surface modification over Fe O NPs by extract biomolecules can
be adjudged from its appearances. There occurs a homogeneous
growth of extract over it. The agglomeration of nanocomposite par-
ticles can be understood due to manual sample preparation.
In order to have information about the elemental composition
of the nanocomposite EDX analysis was carried out. The corre-
sponding profile exhibits Fe, O, C, N and Ag atoms (Fig. 3). It clearly
3 4
Fig. 3. EDX pattern of Fe O @T. spicata/Ag NPs.
Fig. 1. FT-IR spectra of a) Fe
3
O
4 3 4
, b) Thymbra spicata extract and c) Fe O @T. spicata/Ag NPs.
4

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
cubic (111), (200), (220) and (311) planes Ag crystalline phases
[
22]. However, the peak intensities are relatively low due to
extracting coating over the Fe NPs core.
3 4
O
Finally, in order to analyze the electronic environment, oxida-
tion state, and the binding energy of the metallic species, XPS sur-
vey of the Fe O @T. spicata/Ag NPs was carried out. Fig. 6 displays
3 4
the XPS profile of Fe 2p, O 1 s, C 1 s and Ag 3d species. Among the
metallic components, the high-resolution XPS spectra of Fe 2p
were analyzed which revealed two peaks at 712.6 and 726.4 eV,
ascribed to as Fe 2p1/2 and Fe 2p3/2 spin–orbit components respec-
tively. These values indicate towards the magnetite. Similarly, Ag
3
d species comprised of two components, Ag 3d5/2 and Ag 3d3/2,
appeared at 368.8 and 374.8 eV respectively, which directs them
as metallic Ag.
3 4
Magnetic properties of Fe O @T. spicata/Ag NPs nanocomposite
were determined by VSM analysis at room temperature (Fig. 7).
The patterns clearly indicate that they are strongly paramagnetic
in nature. The material exhibits the saturation magnetization
3 4
Fig. 4. TEM image of Fe O @T. spicata/Ag NPs.
(
s
M ) value of 23.7 emu/g. The gradual decrease in magnetization
values are obviously due to the incorporation of extract composites
and diamagnetic Ag respectively. Still, the final material behaves
like a superparamagnet and can be easily attracted by external
magnets.
demonstrates the successful fabrication of the desired nanocom-
posite. Carbon and nitrogen atoms originated from extract that
coated on the surface of magnetic nanoparticles.
The inherent structural features are demonstrated via TEM
study of the nanocomposite. The thin layer of extract surrounding
the black colored Fe
O
3 4
NPs can be visible (Fig. 4). The size of the
3.2. Catalytic application data analysis
composite particles was in accordance with the SEM study and is
around 10–20 nm. The tiny black dots correspond to the Ag NPs,
being of 20–30 nm in size. In addition, the presence of the extract
layer is found effective on in situ reductions and immobilization of
After the meticulous characterizations of Fe O @T. spicata/Ag
3 4
nanocomposite, we turned our attention to explore its catalytic
efficiency. We targeted the one-pot three component synthesis of
the propargylamines by coupling phenyl acetylene, aldehydes
3 4
Ag onto the surface of the Fe O /extract composite. The biomolec-
3
ular conjugate favors the binding of Ag NPs by electrostastic force
of attraction and thereby gets stabilized. These data clearly demon-
strate the proposed architecture of the material.
and amines, commonly known as A coupling. At the outset, stan-
dardization of reaction conditions appeared important and thereby
a probe reaction between phenyl acetylene, benzaldehyde and
morpholine was chosen. A series of experiments were conducted
over the reaction by varying different conditions like solvent, tem-
peratures and catalysts load. The results have been documented in
Table 1. We started the optimizations with the three substrates in
(1.1:1:1) molar ratio in water (3 mL) under heating conditions.
There was no product at all in the absence of catalyst (Table 1,
entry 1). Using a variable load, we obtained a quantitative yield
in the presence of 0.1 mol% of catalysts at 80 °C (entries 3–5 and
13). At lower temperature only a moderate yield was obtained (en-
An X-ray diffraction study of Fe
posites to ascertain the crystalline phases of Ag NPs and Fe
has been shown in Fig. 5. It demonstrates the typical cubic spinel
phase of Fe NPs, the characteristic diffraction peaks are attribu-
3
O
4
@T. spicata/Ag NPs nanocom-
3 4
O
NPs
3 4
O
ted to the (220), (311), (400), (422), (511) and (440) crystal
planes (JCPDS No. 19-0629). This also documents that the function-
alization over Fe
additional peaks due to crystalline Ag NPs. The peaks appeared at
h = 38.3°, 44.3°, 64.2° and 77.1° corresponds to the face centered
3 4
O could not change its crystal structure. The
2
Fig. 5. XRD pattern of (a) fresh Fe
3
O
4
@T. spicata/Ag NPs and (b) recycled catalyst after 8th run.
5

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
3 4
Fig. 6. XPS spectra of Fe O @T. spicata/Ag NPs.
try 2). Now, continuing with the 0.1 mol% catalyst, a screening of
solvent of variable polarity was carried out under boiling condi-
tions (entries 6–10) and found water as the best one, in terms of
eco-friendliness too. Only a poor yield was obtained in solvent-
less conditions (entry 11). Thereby, the best conditions for the
probe reaction were obtained using 0.1 mol% of catalyst in water
at 80 °C (Table 1, entry 3).
hydes and amines were reacted with alkynes to have a library of
propargylamines. The results have been shown in Table 2 (entries
1–20). Except for the aromatic amines (entry 16), all the aliphatic
amines reacted fruitfully regardless the nature of the aldehydes.
Vis-a-vis, all the aromatic, heteroaromatic and aliphatic aldehydes
were highly compatible under the reaction conditions. We also
took the chance to involve aliphatic alkynes (1-octyne) in the reac-
tion, in addition to phenyl acetylenes and they responded well too
(entries 17–20).
The immediate next endeavor was to find the scopes and gener-
ality of those optimized conditions. Thereby, a wide variety of alde-
The plausible mechanistic pathway for the probe A3 reaction
has been depicted in Scheme 2. The reaction is a good example
of a classical CAH activation reaction. The Ag catalyst initially acti-
vates the terminal alkyne CAH bond to from an Ag-acetylide cata-
lyst complex. In the meantime, the 2° amine reacts with the
activated aldehyde to form an imminium intermediate. The former
reactive intermediate then adds up to the imminium ion to afford
the propargylamine derivative in a facile way. The catalyst gets
freed and reused for the next cycle.
In sustainable green heterogeneous catalysis, the simplistic iso-
lation of catalyst and its recycling is a crucial factor. Hence, we
exploited our catalyst in the probe reaction. After completion of
the first cycle, the catalyst was retrieved from the reaction mixture
using a magnet and it was then regenerated by successive cleaning
2
with H O and EtOH and dried at 80 °C for 1 h. Noticeably, we recy-
cled the catalyst for 8 successive times without a considerable
change in its activity (Fig. 8).
We also investigated the true heterogeneous nature of our cat-
alyst by a hot filtration test. In the catalytic process, when the reac-
tion yield reached 55% in halfway of the reaction (4 h), the catalyst
3 4
Fig. 7. VSM analysis for Fe O @T. spicata/Ag NPs.
6

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
Table 1
3 4
The control of experiments towards the optimization of reaction conditions over Fe O
@T. spicata/Ag nanocomposite.a
Entry
Catalyst (mol%)
Solvent
T (°C)
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
9
–
H
H
H
H
H
2
2
2
2
2
O
O
O
O
O
50
50
80
80
80
70
100
80
100
70
24
24
8
–
0.1
0.1
0.06
0.03
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.12
60
96
50
45
30
60
60
96
60
25
96
96
8
24
24
8
8
8
8
8
8
8
CH
DMF
EtOH
Toluene
CH
–
H
H
2
Cl
2
10
11
12
13
3
CN
100
100
80
2
O
O
2
a
Reaction conditions: Benzaldehyde (1.0 mmol), phenylacetylene (1.1 mmol), morpholine (1 mmol), Fe
Yields are based on 1H NMR.
3
O
4
@T. spicata/Ag, solvent (3.0 mL).
b
Table 2
3 4 -
The Fe O @T. spicata/Ag catalyzed A -coupling reaction.
3
a
R1
Amine
R3
Yield (%)b
TON (h )c
ꢂ1
TOF (h )d
ꢂ1
Entry
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
Ph
4-ClC
3-ClC
4-BrC H
6 4
4-OHC
4-MeC
4-OMeC
2-Thiophenyl
2-Furfuryl
Cyclohexyl
C H
3 7
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
Piperidine
Pyrrolidine
Diethyl
Dibenzyl
Aniline
Morpholine
Piperidine
Morpholine
Morpholine
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
n-C
n-C
n-C
n-C
96
96
90
96
85
80
80
90
85
85
80
96
96
85
85
0
960
960
900
960
850
800
800
900
850
850
800
960
960
850
850
0
96
96
90
96
85
80
80
90
85
85
80
96
96
85
85
0
6
H
H
4
6
4
6
H
H
4
6
4
6
H
4
0
1
2
3
4
5
6
7
8
9
0
6
H
6
H
6
H
6
H
13
13
13
13
75
70
85
70
750
700
850
700
75
70
85
70
4-ClC
4-OMeC
6 4
H
6
H
4
a
b
c
Reaction conditions: Aldehyde (1.0 mmol), amine (1 mmol), alkyne (1.1 mmol), Fe
Yields are based on 1H NMR.
TON, turnover number (TON) = Yield/Amount of catalyst (mol).
TOF, turnover frequencies (TOF) = (Yield/Time)/Amount of catalyst (mol).
3 4
O @T. spicata/Ag (20 mg, 0.1 mol%), water (3.0 mL), 80 °C, 10 h.
d
was separated by a magnet from the reaction mixture and the
catalyst-free reaction was allowed to continue. Amusingly, after a
out. This justified the heterogeneity of our catalyst. The TEM image
(Fig. 9) and XRD analysis (Fig. 5b) of the reused catalyst after 8th
cycles confirmed the protection of the catalyst’s nanostructure.
There have been abundant reports being published over this
reaction. The uniqueness of our devised protocol has been vali-
4
h reaction time, there was no further development in the reac-
tion yield. Moreover, the reaction filtrate was studied by ICP-OES
analysis. But there was hardly any trace of silver being leached
7

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
Scheme 2. The plausible reaction pathway for the A3 coupling reaction over Fe
O @T. spicata/Ag.
3 4
expressed in terms of percentage inhibition, has been shown in
Fig. 10.
In the antioxidant test, the IC50 of butylated hydroxytoluene
3 4
and Fe O @T. spicata/Ag nanocomposite were 170 and 139 µg/mL,
respectively (Table 4).
Silver nanoparticles green-mediated show higher antioxidant
effects against free radicals formation into the living system [1-
3
]. The silver nanoparticles green-formulated have excellent redox
properties and have a significant role in free radicals deactivating
2]. Previous researches have indicated that flavonoids and pheno-
[
lic compounds attached to the metallic nanoparticles have signifi-
cant antioxidant properties [2,3].
3 4
Fig. 8. The reuse of Fe O @T. spicata/Ag.
dated by comparing some of the previous results with the current
one, as shown in Table 3. The results clearly indicate the superior-
ity of our work.
3 4
3.3. Antioxidant capacities of Fe O @T. spicata/Ag nanocomposite
Now, turning our attention to investigate the bioactivity of Fe
3
-
O
4
@T. spicata/Ag nanocomposite a concentration-dependent DPPH
radical scavenging effect of nanomaterial was observed against
BHT as a reference. DPPH process is widely applied to determine
the free radical scavenging effect of different antioxidant materials.
The DPPH scavenging abilities are known to be because of the
hydrogen donating activities of antioxidant materials. When DPPH
results are examined, it is observed that it has increased in a dose-
dependent manner [1-3].
The interaction between Fe
and DPPH might have occurred by transferring electrons and
hydrogen ions [2,3]. The scavenging capacity of the Fe @T. spi-
cata/Ag nanocomposite and BHT at different concentrations,
3 4
O @T. spicata/Ag nanocomposite
3 4
O
3 4
Fig. 9. TEM image of recycled Fe O @T. spicata/Ag NPs after 8th run.
8

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
3.4. Cytotoxicity and anti-human colorectal cancer potentials of
Table 4
3 4
The IC50 of Fe O @T. spicata/AgNPs and BHT in the antioxidant test.
3 4
Fe O @T. spicata/Ag nanocomposite
Fe
3
O
4
@T. spicata/AgNPs
BHT
170
In the recent research, the treated cells with several concentra-
tions of the present Fe @T. spicata/Ag nanocomposite were
IC50 (µg/mL)
139
3 4
O
examined by MTT test for 48 h regarding the cytotoxicity proper-
ties on normal (HUVEC) and common colorectal cancer cell lines
i.e., Ramos.2G6.4C10, HCT-8 [HRT-18], and HCT 116.
The absorbance rate was determined at 570 nm, which indi-
cated extraordinary viability on normal cell line (HUVEC) even
up to 1000
and 12).
3 4
lg/mL for Fe O @T. spicata/Ag nanocomposite (Figs. 11
In the case of colorectal cancer cell lines, the viability of them
reduced dose-dependently in the presence of Fe @T. spicata/Ag
nanocomposite. The IC50 of Fe @T. spicata/Ag nanocomposite
were 289, 311, and 174 µg/mL against Ramos.2G6.4C10, HCT-8
HRT-18], and HCT 116 cell lines, respectively (Table 5).
3 4
O
3 4
O
[
Table 3
A catalytic comparison is showing the efficiency of current research in the A3 coupling
(entry 12, Table 2).
Entry Reaction conditions
Temp.
°C)
TOF
(h
Ref.
ꢂ1
(
)
1
2
3
4
5
6
7
8
Fe
AgI, H
3
O
4
@T. spicata/Ag, H
O, N
2
O
80
120
3.3
1.92
0.97
2.72
This work
[5]
[16]
[22]
[23]
[24]
[25]
[26]
2
2
100
100
100
40
Ag NPs, PEG
Ag-NaY, neat
Ag-CIN-1,H
ZnO-IL/Ag, H
PS-NHC-Ag(1),solvent
g-C /Ag(0), EtOH : H
2
O
2
O, 3 h
Reflux 51.1
R.T
O, microwave 80
4
245
3
N
4
2
3 4
Fig. 11. The cell viability of Fe O @T. spicata/Ag NPs against normal (HUVEC) cell
line.
Fig. 10. The antioxidant properties of Fe
3 4
O @T. spicata/AgNPs (A) and BHT (B) against DPPH. The numbers indicate the percent of free radical (DPPH) inhibition in the
concentrations of 0–1000 g/mL of Fe @T. spicata/AgNPs and BHT.
l
3 4
O
9

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
Fig. 12. The anti-human colorectal cancer properties (Cell viability (%)) of Fe
3
O
4
@T. spicata/Ag NPs (Concentrations of 0–1000 µg/mL) against Ramos.2G6.4C10 (A), HCT-8
[
HRT-18] (B), and HCT 116 (C) cell lines. The numbers indicate the percent of cell viability in the concentrations of 0–1000
lg/mL of Fe
3
O
4
@T. spicata/Ag NPs against several
human colorectal cancer cell lines.
Table 5
The IC50 of Fe
3
O
4
@T. spicata/AgNPs in the anti-human colorectal cancer test.
HUVEC
–
Ramos.2G6.4C10
289
HCT-8 [HRT-18]
311
HCT 116
174
IC50 (µg/mL)
Among the different parameters of metallic nanoparticles such
as, size, texture and nature of surface functions, the size effect is
most essential in the anticancer assay using standard cancer cell
lines. Previous reports revealed that the anticancer activity
increases with a decrease in particle size based on their better pen-
etration ability over the cell lines. It has been surveyed that particle
size lower than 50 nm displays better activity in the corresponding
cancer cell lines [2,3].
mary carcinoma, uterus cancer, lung epithelial cancer, Lewis lung
carcinoma, colon cancer, and human glioma [2,3].
Likely significant anti-human colorectal cancer potentials of
3 4
Fe O @T. spicata/Ag nanocomposite against common colorectal
cancer cell lines i.e., Ramos.2G6.4C10, HCT-8 [HRT-18], and HCT
116 are linked to their antioxidant effects. Similar reports have
indicated the antioxidant materials such as metallic nanoparticles
especially silver nanoparticles reduce the volume of tumors by
removing free radicals [43].
3
As shown in Figs. 2 and 4 of our study, the average size of Fe -
O
4
@T. spicata/Ag nanocomposite is lower than 50 nm.
In detail, the high presence of free radicals in the normal cells
make many mutations in their DNA and RNA, destroy their gene
In the anticancer effects of silver nanoparticles, they have been
used to treat several cancers including human lung cancer, mam-
10

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
expression and then accelerate the proliferation and growth of
abnormal cells or cancerous cells [43,44].
Acknowledgments
The free radicals high presences in all cancers such as breast,
gallbladder, stomach, rectal, liver, gastrointestinal stromal, esopha-
geal, bile duct, small intestine, pancreatic, colon, parathyroid, thy-
roid, bladder, prostate, testicular, fallopian tube, vaginal,
hypopharyngeal, throat, lung, and skin cancers indicate the signif-
icant role of these molecules in making angiogenesis and tumori-
genesis [44,45].
Many researchers reported that silver nanoparticles green-
synthesized have the remarkable role in removing free radicals
and growth inhibition of all cancerous cells [46,47].
This project also was supported by Researchers Supporting Pro-
ject number (RSP-2020/103) King Saud University, Riyadh, Saudi
Arabia.
References
[
1] (a) A. Ghashghaii, M. Hashemnia, Z. Nikousefat, M.M. Zangeneh, A. Zangeneh,
Pharmaceut. Sci. 23 (2017) 256–263;
(
b) S. Goorani, N. Shariatifar, N. Seydi, A. Zangeneh, R. Moradi, B. Tari, F. Nazari,
M.M. Zangeneh, Oriental Pharm. Exp. Med. 19 (2019) 403–413;
(c) A.R. Jalalvand, M. Zhaleh, S. Goorani, M.M. Zangeneh, N. Seydi, A. Zangeneh,
R. Moradi, J. Photochem. Photobiol., B 192 (2019) 103–112;
(
d) R. Moradi, M. Hajialiani, S. Salmani, M. Almasi, A. Zangeneh, M.M.
Zangeneh, Comp. Clin. Pathol. 28 (2019) 1205–1211;
e) K. Rashidi, M. Mahmoudi, G. Mohammadi, M.M. Zangeneh, S. Korani, H.C.
4
. Conclusion
(
Goicoechea, H.-W. Gu, A.R. Jalalvand, Int. J. Biol. Macromol. 120 (2018) 587–
595;
Finally, we like to conclude to introduce a green method by
(
f) H. Sherkatolabbasieh, L. Hagh-Nazari, S. Shafiezadeh, N. Goodarzi, M.M.
plant extract for modification of magnetic nanomaterial by the
aim of ultrasonic energy that then could be used as magnetic
reducing absorbent to Ag NPs being decorated over its surface. Fol-
low by this way, we synthesized Fe O @T. spicata/Ag NPs
3 4
nanocomposite for the first time using Thymbra spicata extract.
Zangeneh, A. Zangeneh, Arch. Biol. Sci. 69 (2017) 535–543.
2] (a) M. Abdoli, K. Sadrjavadi, E. Arkan, M.M. Zangeneh, S. Moradi, A. Zangeneh,
M. Shahlaei, S. Khaledian, J. Drug Deliv. Sci. Technol. 60 (2020) 102044;
[
(
1
(
b) L. Dou, X. Zhang, M.M. Zangeneh, Y. Zhang, Bioorg. Chem. 106 (2020)
04468;
c) Y. Han, Y. Gao, X. Cao, M.M. Zangeneh, S. Liu, J. Li, Int. J. Biol. Macromol. 164
The structural features were analyzed through a wide range of ana-
(2020) 2974–2986;
lytical techniques. The Fe
3
O
4
@T. spicata/Ag nanocatalyst was uti-
multicomponent synthesis of
(d) M. Ishaq, P. Taslimi, Z. Shafiq, S. Khan, R.E. Salmas, M.M. Zangeneh, A.
Saeed, A. Zangeneh, N. Sadeghian, A. Asari, H. Mohamad, Bioorg. Chem. 100
lized in the one-pot
(
(
2020) 103924;
3
propargylamines by A coupling under solvent-free condition.
The role of immobilized Ag NP in the reaction pathway was vali-
dated by investigating the Ag-free catalyst component in the reac-
tion, which ended up with low productivity. The catalyst was
reused for 8 consecutive cycles without momentous loss of its
reactivity. There was also negligible leaching of Ag species in the
reaction medium, thereby proving its robustness.
e) Y. Li, N. Li, W. Jiang, G. Ma, M.M. Zangeneh, Int. J. Biol. Macromol. 163
(2020) 2162–2171.
[
3] (a) B. Mahdavi, S. Paydarfard, M.M. Zangeneh, S. Goorani, N. Seydi, A.
Zangeneh, Appl. Organomet. Chem. 34 (2020) e5248;
(
b) B. Mahdavi, S. Saneei, M. Qorbani, M. Zhaleh, A. Zangeneh, M.M. Zangeneh,
E. Pirabbasi, N. Abbasi, H. Ghaneialvar, Appl. Organomet. Chem. 33 (2019)
e5164;
(
c) N. Seydi, B. Mahdavi, S. Paydarfard, A. Zangeneh, M.M. Zangeneh, F. Najafi,
A.R. Jalalvand, E. Pirabbasi, Appl. Organomet. Chem. 33 (2019) e5009;
(d) A. Sujayev, P. Taslimi, E. Garibov, M. Karaman, M.M. Zangeneh, Bioorg.
Chem. 104 (2020) 104216;
The Fe
colorectal cancer activities dose-dependently without any cytotox-
icity on the normal cell line (HUVEC). Also, the Fe @T. spicata/Ag
nanocatalyst revealed excellent antioxidant properties against
common free radicals, i.e. DPPH. It appears the Fe @T. spicata/
3 4
O @T. spicata/Ag nanocatalyst had effective anti-human
(
e) T. Sun, J. Gao, H. Shi, D. Han, M.M. Zangeneh, N. Liu, H. Liu, Y. Guo, X. Liu,
3 4
O
Int. J. Biol. Macromol. 165 (2020) 787–795;
(f) R. Tahvilian, M.M. Zangeneh, H. Falahi, K. Sadrjavadi, A.R. Jalalvand, A.
Zangeneh, Appl. Organomet. Chem. 33 (2019) e5234.
3 4
O
[
[
4] M.B. Gawande, P.S. Branco, R.S. Varma, Chem. Soc. Rev. 42 (2013) 3371–3393.
5] S. Sadjadi, P. Mohammadi, M.M. Heravi, Sci. Rep. 10 (2020) 6535–6544.
[6] S. Sanli, F. Ghorbani-Zamani, H. Moulahoum, Z.P. Gumus, H. Coskunol, D.O.
Demirkol, S. Timur, Anal. Chem. 92 (2020) 1033–1040.
Ag nanocatalyst can be used as novel chemotherapeutic supple-
ments or drugs for the treatment of several types of colorectal can-
cers in humans soon.
[
[
[
7] L.M. Rossi, N.J.S. Costa, F.P. Silva, R. Wojcieszak, Green Chem. 16 (2014) 2906–
933.
Funding (Name of the fund, subsidy number):
2
8] T. Tamoradi, H. Veisi, B. Karmakar, J. Gholami, Mater. Sci. Eng. C 107 (2020)
110260–110270.
9] S. Hemmati, M. Hekmati, D. Salamat, M. Yousefi, B. Karmakar, H. Veisi,
Polyhedron 179 (2020) 114359–114364.
10] H. Veisi, M. Ghorbani, S. Hemmati, Mater. Sci. Eng. C. 98 (2019) 584–593.
[11] H. Veisi, M. Pirhayati, A. Kakanejadifard, P. Mohammadi, M.R. Abdi, J. Gholami,
S. Hemmati, Chem. Select. 3 (2018) 1820–1826.
–
–
–
National Natural Science Foundation of China for Young Schol-
ars, 82003865.
Application research of the Science and Technology Department
in Sichuan province, 21YYJC2810 (2021YJ0461).
New seed research fund of West China Second University Hospi-
tal, KX095.
[
[
12] H. Veisi, T. Ozturk, B. Karmakar, T. Tamoradi, S. Hemmati, Carbohydr. Polym.
35 (2020) 115966.
2
[
[
[
13] H. Veisi, S. Hemmati, P. Safarimehr, J. Catal. 365 (2018) 204–212.
14] E. Farzad, H. Veisi, J. Indus. Eng. Chem. 60 (2018) 114–124.
CRediT authorship contribution statement
15] M.R. Awual, M. Khraisheh, N.H. Alharthi, M. Luqman, A. Islam, M. Rezaul
Karim, M.M. Rahman, M.A. Khaleque, Chem. Eng. J. 343 (2018) 118–127.
16] P. Mohammadi, M.M. Heravi, S. Sadjadi, Sci. Rep. 10 (2020) 6579–6588.
17] G. Aguilera, C.C. Berry, R.M. West, E. Gonzalez-Monterrubio, A. Angulo-molina,
Ó. Arias-Carrión, et al., Nanoscale Adv. 1 (2019) 671–685.
[
[
Tian Tang: Visualization, Writing - original draft, Formal analy-
sis. Qingjie Xia: Visualization, Writing - original draft, Formal anal-
ysis. Junliang Guo: Visualization, Writing - original draft, Formal
analysis. Arunachalam Chinnathambi: Funding acquisition,
Methodology, Supervision. Sara T. Alrashood: Funding acquisition,
Methodology, Supervision. Sulaiman Ali Alharbi: Funding acquisi-
tion, Methodology, Supervision. Jie Zhang: Funding acquisition,
Methodology, Supervision, Formal analysis, Writing - review &
editing.
[18] M. Esmaeilpour, A.R. Sardarian, H. Firouzabadi, J. Organometal. Chem. 873
2018) 22–34.
(
[
[
19] S. Lotfi, H. Veisi, Mater. Sci. Eng. C 105 (2019) 110112–110122.
20] Y. Ding, S.Z. Shen, H. Sun, K. Sun, F. Liu, Y. Qi, J. Yan, Mater. Sci. Eng. C 48 (2015)
(2015) 487–498.
[21] X. Cao, C. Tan, M. Sindoro, H. Zhang, Chem. Soc. Rev. 46 (2017) 2660–2677.
[
22] H. Veisi, L. Mohammadi, S. Hemmati, T. Tamoradi, P. Mohammadi, ACS Omega
(2019) 13991–14003.
4
[
[
[
[
[
[
23] H. Veisi, S.B. Moradi, P. Safarimehr, Mater. Sci. Eng. C 100 (2019) 445–452.
24] H. Veisi, S. Azizi, P. Mohammadi, J. Clean. Prod. 170 (2018) 1536–1543.
25] R.R. Qiao, C.H. Yang, M.Y. Gao, J. Mater. Chem. 19 (2009) 6274–6293.
26] S. Prabhu, E.K. Poulose, Int. Nano Lett. 2 (2012) 32.
27] M. Zhu, C. Wang, D. Meng, G. Diao, J. Mater. Chem. A. 1 (2013) 2118–2125.
28] C.H. Liu, Z.D. Zhou, X. Yu, B.Q. Lv, J.F. Mao, D. Xiao, Inorg. Mater. 44 (2008) 291–
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
295.
[
29] H. Veisi, S. Taheri, S. Hemmati, Green Chem. 18 (2016) 6337–6348.
[30] H. Veisi, A. Mirzaei, P. Mohammadi, RSC Adv. 9 (2019) 41581–41590.
11

T. Tang, Q. Xia, J. Guo et al.
Journal of Molecular Liquids 338 (2021) 116451
[
[
[
[
31] H. Veisi, T. Tamoradi, B. Karmakar, S. Hemmati, J. Phys. Chem. Solids 138
2020) 109256–109262.
32] M. Nodehi, M. Baghayeri, R. Ansari, H. Veisi, Mater. Chem. Phys. 244 (2020)
22687–122697.
33] H. Veisi, S. Razeghi, P. Mohammadi, S. Hemmati, Mater. Sci. Eng. C 97 (2019)
24–631.
34] S. Mirfakhraei, M. Hekmati, F. Hosseini Eshbala, H. Veisi, New J. Chem. 42
2018) 1757–1761.
[41] M.-W. Chen, B. Wu, Z.-P. Chen, L. Shi, Y.-G. Zhou, Org. Lett. 18 (2016) 4650–
4653.
(
[42] S. Ramesh, R. Nagarajan, Tetrahedron 69 (2013) 4890–4898.
[43] L. Katata-Seru, T. Moremedi, O.S. Aremu, et al., Green synthesis of iron
nanoparticles using Moringa oleifera extracts and their applications: Removal
of nitrate from water and antibacterial activity against Escherichia coli, J. Mol.
Liq. 256 (2018) 296–304.
[44] S. Sangami, M. Manu, Synthesis of Green Iron Nanoparticles using Laterite and
their application as a Fenton-like catalyst for the degradation of herbicide
Ametryn in water, Environ. Technol. Innov. 8 (2017) 150–163.
[45] N. Beheshtkhoo, M.A.J. Kouhbanani, A. Savardashtaki, et al., Green synthesis of
iron oxide nanoparticles by aqueous leaf extract of Daphne mezereum as a
novel dye removing material, Appl. Phys. A 124 (2018) 363–369.
[46] I.A. Radini, N. Hasan, M.A. Malik, et al., Biosynthesis of iron nanoparticles using
Trigonella foenum-graecum seed extract for photocatalytic methyl orange dye
degradation and antibacterial applications, J. Photochem. Photobiol. B 183
(2018) 154–163.
1
6
(
[
[
35] H. Veisi, S. Najafi, S. Hemmati, Int. J. Biol. Macromol. 113 (2018) 186–194.
36] H. Veisi, M. Ghadermaji, A. Naderi, Appl. Organometal. Chem. 30 (2016) 341–
3
45.
[
37] H. Veisi, Polyhedron 159 (2019) 212–216.
[
38] K. Lauder, A. Toscani, N. Scalacci, D. Castagnolo, Chem. Rev. 117 (2017) 14091–
1
4200.
[
39] O. Cortezano-Arellano, M.A. Hernández-Gasca, D. Ángeles-Beltrán, G.E.
NegrónSilva, R. Santillan, Tetrahedron Lett. 59 (2018) 2403–2406.
[
40] V.A. Peshkov, O.P. Pereshivko, E.V. Van der Eycken, Chem. Soc. Rev. 41 (2012)
3
790–3807.
[47] G. Oganesvan, A. Galstyan, V. Mnatsakanyan, et al., Phenolic and flavonoid
compounds of Ziziphora clinopodioides, Chem. Nat. 27 (1991) 247.
12