Received: 23 September 2019 Revised: 5 January 2020 Accepted: 15 January 2020

DOI: 10.1002/aoc.5560

FULL PAPER

Design and characterization of Fe3O4/GO/Au-Ag

nanocomposite as an efficient catalyst for the green
synthesis of spirooxindole-dihydropyridines

Sara Kavyani | Robabeh Baharfar

Faculty of Chemistry, University of

Mazandaran, 4741695447, Babolsar, Iran
Correspondence
Robabeh Baharfar, Faculty of Chemistry,
University of Mazandaran, Babolsar, Iran.
Email: baharfar@umz.ac.ir
A novel magnetic nanocomposite of Au-Ag nanoparticles anchored on Fe3O4/
graphene oxide spheres (Fe3O4/GO/Au-Ag) was successfully fabricated by the
layer-by-layer assembly technique. The prepared Fe3O4/GO/Au-Ag was fully
characterized by Fourier-transform infrared (FT-IR) spectroscopy, X-ray dif-
fraction (XRD) analysis, thermogravimetric analysis (TGA), field-emission
scanning electron microscopy (FE-SEM), energy-dispersive x-ray spectroscopy
(EDS), transmission electron microscopy (TEM), and Raman spectroscopy.
This nanocomposite showed unique catalytic performance for the synthesis of
Spiro[indoline-3,50 -pyrido[2,3-d:6,5-d’]dipyrimidine]-pentaone derivatives by
the three-component condensation reaction of isatins, barbituric acids and
6-amino uracil at room temperature and in aqueous media. The significant
advantages of this protocol include highly stable, easily separable and reusable
catalyst, simple operation, environmental friendliness and excellent yields.

KEYWORDS
graphene oxide, magnetic nanocomposite, multicomponent reactions, nanoparticles,
spirooxindole

1 | INTRODUCTION into a unit system, many functional properties of these

Metallic nanoparticles have unique chemical and physi-
cal characteristics for potential applications in various
areas such as optics,[1] catalysis,[2] biomedicine,[3] and
sensors.[4] Moreover, the combination of two or multiple
metal nanoparticles into a unit entity is more beneficial
for numerous applications than a monometallic entity. In
particular, bimetallic nanoparticles have shown excellent
catalytic activity compared with that of monometallic
nanoparticles in a wide range of reactions.[5–8] Among
the known metal nanoparticles, gold and silver
nanoparticles, have gained considerable attention
because of their widespread range of application such as
photonics,[9] catalysis,[10] biological assays,[11] sensing,[12]
information storage,[13] and surfaced-enhanced Raman
scattering (SERS).[14] By incorporating Au and Ag metals
materials would be superior to their corresponding single
metal ones in terms of catalytic activities due to the syn-
ergistic effects of two metals.[15–17] Gold and silver have
the same face center cubic (fcc) crystal arrangement and
lattice spacing, so they can form alloy very easily.[18]
Many preparation techniques have been developed for
the synthesis of Au-Ag bimetallic nanoparticles, such as
co-reduction,[19] evaporation-condensation,[20] galvanic
replacement reactions,[21] and sonochemical deposi-
tion.[22] Shin et al. reported the preparation of Au–Ag
alloy nanoparticles on cellulose nanocrystals by a co-
reduction chemical method using sodium citrate as the
reducing agent.[23] Liu et al. synthesized Au–Ag bimetal-
lic nanoparticles supported on silica gel via galvanic
replacement reaction.[24] Anandan et al. reported the
preparation of Au–Ag bimetallic nanoparticles by the

Appl Organometal Chem. 2020;e5560. wileyonlinelibrary.com/journal/aoc © 2020 John Wiley & Sons, Ltd. 1 of 15
https://doi.org/10.1002/aoc.5560
2 of 15
sonochemical technique in the presence of polymer
stabilizer.[25]
Due to the susceptible of metal nanoparticles to irre-
versible aggregation, their catalytic activity decreases
notably. Therefore, metal nanoparticles are often
immobilized onto supporting materials such as metal–
organic frameworks,[26] various polymer matrices,[27] and
carbon spheres[28] to prevent the aggregation, increase
the stability, facilitate the recovery and enhance the cata-
lytic performance. Graphene is a flat single layer of car-
bon atoms, arranged in a hexagonal honeycomb
lattice.[29,30] In recent years, Graphene oxide (GO), a
derivative of graphene, has been used as solid support for
nanoparticles due to its many exceptional properties such
as large specific surface area, high carrier mobility, sim-
ple and cheap process of manufacturing and chemical
stability.[31] Many monometallic and bimetallic
nanoparticles such as Au,[32] TiO2,[33] ZnO,[34] Pd,[35]
Ag,[36] and Au-Pt[37] have been successfully deposited on
graphene oxide. Most recently, graphene oxide supported
bimetallic nanoparticles, used as an efficient catalyst for
organic conversions.[38–40]
On the other hand, magnetic materials have been
widely studied for various applications due to their
unique properties such as large surface area, non-toxicity,
low cost and easy separation by external magnetic
fields.[41] Recently, the combination of magnetic particles
with other materials to form Fe3O4-based composites has
attracted high attention due to the broad application in
the separation sciences. Lin et al. reported the prepara-
tion of Au-Fe3O4 heterostructures as magnetic recyclable
catalyst for the reduction of nitrophenols.[42] Yang et al.
anchored TiO2 nanoparticles on reduced graphene oxide
encapsulated Fe3O4 spheres (Fe3O4@rGO@TiO2) as a
high efficient reusable catalyst for the photo-Fenton sys-
tem.[43] Magnetic-based composites with a core-shell
structure that were designed by Fe3O4 particles as core
and GO nanosheets as shell, not only are easily separated
from the reaction system, but also to afford the stable
sphere for supporting of metallic nanoparticles.[44,45]
As is known, spirocyclic oxindole frameworks repre-
sent an important class of natural alkaloids and unnatu-
ral compounds, many of which exhibit broad biological
and pharmacological properties such as antimicrobial,[46]
antiviral,[47] and anticancer.[48] On the other hand,
pyrimidine and its derivatives have been attracted great
attention for their biological activities and clinical appli-
cations.[49] Among heterocyclic compounds fused with a
pyrimidine, spirocyclic pyrido-pyrimidine moieties are of
special importance in drug discovery research. In addi-
tion, compounds containing dihydropyridine scaffolds
are one of the important targets in organic synthesis due
to their broad range of pharmacological and therapeutic
KAVYANI AND BAHARFAR
potential. Many of the medications such as nifedipine,
nicardipine, and felodipine belong to the dihydropyridine
type of calcium channel blockers used to treat hyperten-
sion and angina pectoris.[50–52] Therefore, research for a
novel and efficient methodology for the preparation of
spiro-dihydropyridine compounds with minimum syn-
thetic steps in green conditions has gained considerable
interest in modern organic and pharmaceutical
chemistry.
Multicomponent reactions being efficient and effec-
tive methods for the synthesis of heterocyclic scaffolds
from several diversity elements in a one pot operation
with high degree of selectivity, diversity, synthetic con-
vergence and atom-economy.[53–55] In recent decades,
design of new MCRs with employing catalyst and the
green solvent has attracted much attention. Khurana
et al. have reported a multicomponent reaction in the
presence of InCl3 as a recyclable catalyst to produce a
variety of bioactive pyrimidine derivatives in water.[56]
Dandia et al. reported a novel and efficient three-
component reaction for the synthesis of structurally com-
plex spirooxindole derivatives catalyzed by ZnS
nanoparticles in an aqueous medium.[57] The green
method in the synthetic processes is determined by many
factors such as the clean and accessible of solvent, energy
efficiency in the reaction stages, use of the safe and reus-
able catalytic reagents, and atom economy. In this way
during the last two decades, green principles have been
highly regarded in chemical processes. Nasrollahzadeh
et al. reported a green protocol for the synthesis of
1-carbamoyl-1-phenylureas in the presence of a recycla-
ble and reusable Fe3O4@SiO2 nanocatalyst in water as a
green solvent.[58] Sajjadi et al. synthesized the magneti-
cally nanocomposites using plant extracts and non-toxic
solvents as green and non-corrosive nanocatalysts.[59,60]
Considering the above reports and in continuation of
our previous studies in the development of the simple
and effective multicomponent reactions for the synthesis
of novel heterocyclic compounds by heterogeneous
catalysts,[61–63] we wish to report a facile route to fabrica-
tion of Fe3O4/GO/Au-Ag nanocomposite, which exhibits
superior catalytic activity for the efficient preparation of
Spiro[indoline-3,50 -pyrido[2,3-d:6,5-d’]dipyrimidine]-
pentaone derivatives from a wide diversity of isatin,
6-aminouracil and different 1,3-dicarbonyl compounds in
water under green and mild reaction conditions. Many of
methods reported for the synthesis of spirooxindole com-
pounds suffer from disadvantages such as high
temperature,[64] use of homogeneous catalyst,[65] long
reaction times,[66] and the use of harmful organic sol-
vent.[67] According to the principles presented in green
chemistry in this study, the reactions for the synthesis of
spirooxindole were carried out in the water as the green
FE3O4/GO/AU-AG CATALYST FOR SYNTHESIS OF SPIROOXINDOLE
solvent with advantages such as easy availability, non-
toxic, neutral and natural, non-corrosive, and inexpen-
sive solvent. The synthetic reactions were performed at
ambient temperature and pressure, so the energy require-
ment was minimized. Also, these reactions are a one-pot
multicomponent operation with a high atom economy
and water was a by-product in these reactions. Further-
more, the syntheses of spirooxindoles were accomplished
in the presence of a recyclable heterogeneous catalyst as
a promising option for green chemistry. On the other
hand, Compared with the numerous chemical and
biological[68–70] methods reported on the synthesis of
metallic nanoparticles, our method for the synthesis of
Au-Ag nanoparticles has several features including no
need of higher temperature and calcination, mild reac-
tion condition, simple procedure, use of the non-toxic sol-
vent and short process.
2 | R ES U L T S A N D D I S C U S S I O N
Step-by-step pathway for the synthesis of hierarchical
Fe3O4/GO/Au-Ag nanocomposite is schematically illus-
trated in Scheme 1. Fe3O4 particles were first modified
with a thin layer of tetraethyl orthosilicate (TEOS),
followed by the treatment with (3-aminopropyl)
triethoxysilane (APTES) to endow abundant amino
groups on their surface, which can help the Fe3O4
spheres combine with the GO nanosheets via covalent
bonding. Next, the Au-Ag bimetallic nanoparticles were
deposited over the GO nanosheets by co-reduction
method, in which AgNO3 and HAuCl4 were chosen as
Ag and Au nanoparticles precursor and also citrate and
cetyltrimethylammonium bromide (CTAB) were applied
as reducing agent and cationic surfactant, respectively.
Figure 1 shows the FT-IR spectra of naked Fe3O4,
Fe3O4/GO and Fe3O4/GO/Au-Ag. The Fe-O vibrational
band of pristine Fe3O4 appeared at 582 cm−1 (Figure 1a).
After coated with TEOS, APTES and GO new absorption
peaks appeared in the FT-IR spectra. The observed peaks
at 1068 and 2922 cm−1 are related to Si-O-Si and aliphatic
chain stretching vibrations that indicate successful modi-
fication of Fe3O4, and the peaks placed at 1387 and
SCHEME 1 Different steps for synthesis of Fe3O4/GO/Au-Ag
3 of 15
1624 cm−1 can be indexed to C-N and C=O vibration,
which confirms successfully covalent encapsulation of
Fe3O4 particles with GO nanosheet through the amide
linkages (Figure 1b). In spectrum of Fe3O4/GO/Au-Ag,
the intensity of absorption peaks at 1065, 1390 and
1630 cm−1 were decreased in comparison with the FT-IR
spectrum of Fe3O4/GO, which can be attributed to the
formation of Au-Ag nanoparticles on the surface of
Fe3O4/GO. Also, the absorption peaks located at around
1581 and 2852 cm−1 indicate that the CTAB and citrate
remained on the Au-Ag nanoparticles surface
(Figure 1c).
Structural analysis and morphology of the synthe-
sized Fe3O4/GO and Fe3O4/GO/Au-Ag were character-
ized by FE-SEM and TEM measurements. Also,
elemental analysis of Fe3O4/GO/Au-Ag was accom-
plished by Energy-dispersive X-ray (EDX) analyzer. The
SEM images of Fe3O4/GO and Fe3O4/GO/Au-Ag are
shown in Figure 2. After the magnetic particles were
wrapped with silk-like GO nanosheet, the Fe3O4/GO par-
ticles showed wrinkled and rough outward surface
(Figure 2a). The SEM image of Fe3O4/GO/Au-Ag proved
that the Au-Ag nanoparticles were anchored and fixed on
the surface of Fe3O4/GO particles (Figure 2b and c).
The EDX spectrum of the Fe3O4/GO/Au-Ag showed
the content of Fe, O, C, Au and Ag signal peaks, which
confirms Fe3O4/GO/Au-Ag particles were successfully
formed (Figure 3).
TEM images of Fe3O4/GO/Au-Ag also clearly illus-
trated Au-Ag nanoparticles were successfully supported
on the Fe3O4/GO particles and the average size of the
Au-Ag nanoparticles are around 15 nm (Figure 4a and b).
The structures of the as-synthesized Fe3O4/GO and
Fe3O4/GO/Au-Ag particles were characterized by XRD as
shown in Figure 5. The XRD pattern of Fe3O4/GO is very
similar to that of the pristine Fe3O4 (Figure 5a). The dif-
fraction peaks at 2θ = 30.3 , 35.7 , 43.4 , 53.8 , 57.4 and
62.9 are ascribed to the (220), (311), (400), (422), (511),
and (440) lattice planes of the pure cubic spinel crystal
structure of Fe3O4. However, no diffraction peak of GO is
apparent for the as-synthesized Fe3O4/GO particle. It
should be noted that the phase of the Fe3O4 particles
nearly has no changes during the wrapped with GO. As
4 of 15
FIGURE 2 SEM images of (a) Fe3O4/GO, and (b and c) Fe3O4/GO/Au-Ag,
to the Fe3O4/GO/Au-Ag, some new peaks also appeared
at 2θ = 38.5 , 44.6 , 64.7 and 77.8 are corresponded to
the (111), (200), (220) and (311) which were indicative
the crystal plane of Au-Ag bimetallic nanoparticles
(Figure 5b).
The TGA analysis curves of Fe3O4/GO and Fe3O4/
GO/Au-Ag are shown in Figure 6. The Fe3O4/GO parti-
cles demonstrate a total weight loss of 12% at 100–600  C,
KAVYANI AND BAHARFAR
FIGURE 1 FT-IR spectra of (a) Fe3O4,
(b) Fe3O4/GO, and (c) Fe3O4/GO/Au-Ag
which are ascribed to the removal of adsorbed water and
decomposition and vaporization of different oxygen-
containing functional groups at various sites on the sur-
face of the Fe3O4/GO (Figure 6a). Whereas, the Fe3O4/
GO/Au-Ag particles showed two weight loss steps with
different rates (Figure 6b). The first slow weight loss step
is before 120  C related to the elimination of water mole-
cules. The second sharp weight loss step at 120–600  C
FE3O4/GO/AU-AG CATALYST FOR SYNTHESIS OF SPIROOXINDOLE
FIGURE 3 EDS spectrum of Fe3O4/
GO/Au-Ag
F I G U R E 4 TEM images of (a) Fe3O4/
GO/Au-Ag, and (b) Au-Ag nanoparticles
FIGURE 5 XRD patterns of (a) Fe3O4/GO, and (b) Fe3O4/
GO/Au-Ag
can be attributed to the decomposition of the surfactant
and oxygen-containing functional groups.
Raman spectroscopy is a powerful technique for iden-
tification and characterization of carbonaceous materials.
The Raman spectrum of Fe3O4/GO/Au-Ag demonstrated
of two prominent bands at around 1361 and 1593 cm−1,
5 of 15
FIGURE 6 TGA analyses of (a) Fe3O4/GO, and (b) Fe3O4/
GO/Au-Ag
which are assigned to the D (arising from primary
stretching of sp2 bonded carbon atoms) and G (originate
from the disordered carbon atoms) bands of the GO
nanosheets (Figure 7).
At the outset, the multicomponent reaction of isatin
(1 mmol), 6-amino uracil (1 mmol) and barbituric acid
(1 mmol) affording spirooxindole, was selected as
6 of 15 KAVYANI AND BAHARFAR

different catalysts, solvents and temperatures and the

FIGURE 7 Raman spectra of Fe3O4/GO/Au-Ag
template reaction to investigate the catalytic activity of
Fe3O4/GO/Au-Ag nanocomposite. To explore the optimal
conditions, the model reaction was checked with
results of this study are illustrated in Table 1.
In the absence of catalyst no reaction occurred even
after 24 hr under reflux in ethanol or water (Table 1,
entry 1, 2). The model reaction carried out using FeCl3,
AlCl3, p-TSA and ZnCl2 as catalyst and their catalytic
effects were moderate (Table 1, entry 3–6). By performing
the model reaction with Fe3O4/GO/Au-Ag in ethanol the
product yield increased to 78% in a shorter reaction time
(Table 1, entry 15). The reaction proceeded more effi-
ciently in the presence of Fe3O4/GO/Au-Ag in various
solvents such as MeOH, EtOH, DMF and H2O (Table 1,
entry 15–19). Also the temperature effect was examined
at room temperature and reflux in water (Table 1, entry
18–19). It was found that in the presence of Fe3O4/
GO/Au-Ag nanocomposite and in water as the selected

TABLE 1 Optimization of reaction conditions

Entry Conditiona Catalystb Time [hr] Yield [%]c TON

1 H2O (reflux) ------ 24 trace ------
2 EtOH (reflux) ------ 24 trace ------
3 EtOH (reflux) FeCl3 24 30 2.4
4 EtOH (reflux) AlCl3 24 35 2.3
5 EtOH (reflux) ZnCl2 24 40 2.7
6 H2O (reflux) p-TSA 12 70 6.0
7 H2O (reflux) Fe3O4 24 trace ------
8 H2O (reflux) GO 24 20 ------
9 H2O (reflux) Fe3O4/GO 24 20 ------
10 H2O (reflux) Au-Ag 6 70 11.6
11 H2O (reflux) Fe3O4/Au-Ag 6 50 98.5
12 H2O (reflux) GO/Au-Ag 6 55 102.2
13 H2O (reflux) Fe3O4/GO/Au 6 60 107.4
14 H2O (reflux) Fe3O4/GO/Ag 6 50 67.4
15 EtOH (reflux) Fe3O4/GO/Au-Ag 5 78 142.2
16 MeOH (reflux) Fe3O4/GO/Au-Ag 5 75 136.7
17 DMF (reflux) Fe3O4/GO/Au-Ag 5 72 131.3
18 H2O (reflux) Fe3O4/GO/Au-Ag 2 80 145.9
19 H2O (rt) Fe3O4/GO/Au-Ag 2 90 164.1
a
Reaction conditions: isatin (1 mmol), barbituric acid (1 mmol), 6-amino uracil (0.12 g, 1 mmol).
b
20 mg of catalyst was used.
c
Isolated yield.
FE3O4/GO/AU-AG CATALYST FOR SYNTHESIS OF SPIROOXINDOLE
solvent the desired product was obtained in excellent
yield and high purity at room temperature (Table 1, entry
19). A comparison of Fe3O4/GO/Au-Ag with Fe3O4/Au-
Ag and GO/Au-Ag resulted that GO nanosheet not only
prevents the aggregation of Au-Ag nanoparticles but also
improves the catalytic activity (Table 1, entry 11), and
also without Fe3O4, the GO nanosheet and Au-Ag
nanoparticles aggregate and precipitate quickly, thus the
catalytic performance of GO/Au-Ag is nearly low
(Table 1, entry 12). The Fe3O4/GO/Au-Ag indicated a
much higher catalytic activity than Fe3O4/GO/Au and
Fe3O4/GO/Ag counterpart under the same conditions
(Table 1, entry 13, 14). The electron transfer of gold
atoms on the silver atoms can increase the electron den-
sity on the surface of the Au-Ag nanoparticles and
improve the catalytic activity.
The required amount of catalyst for this reaction,
which gave the best yields, was 20 mg (Table 2).
T A B L E 2 Effect of the catalyst amount on the synthesis of
spirooxindole-dihydropyridinesa
Entry Amount [mg] Yield [%]b
1 5 40
2 10 67
3 15 86
4 20 90
5 25 90
a
Reaction conditions: isatin (1 mmol), barbituric acid (1 mmol), 6-amino
uracil (0.12 g, 1 mmol), H2O (5 ml), catalyst (Fe3O4/GO/Au-Ag), rt, 2 hr.
b
Isolated yield.
c
TOF was calculated for the first hr of reaction.
FIGURE 8 Diversity of starting material
7 of 15
Accordingly, performing the reaction in the presence of
20 mg of nanocatalyst (Fe3O4/GO/Au-Ag) in water at
room temperature was chosen as the optimal condition.
The scope of this methodology was evaluated using
6-amino uracil, isatin derivatives and different barbituric
acids (Figure 8) under the optimized reaction conditions.
Interestingly, a diverse range of substrates underwent
a smooth transformation and the desired spirooxindole
products were obtained in good to excellent yields
(Table 3). It was found, in the presence of the Fe3O4/
GO/Au-Ag nanocomposite as a catalyst, the reaction
times and yields of some spirooxindole derivatives were
improved in comparison with the previous report at the
same solvent and temperature.[71]
A plausible mechanism for the formation of
spirooxindole derivatives from this three component
reaction is proposed in Scheme 2. The Knoevenagel con-
densation of 6-aminouracil with isatin in the presence of
Fe3O4/GO/Au-Ag as a dual role catalyst afforded the
intermediate 6-imino-5-(2-oxoindolin-3-ylidene)dihydro-
pyrimidine-2,4-dione (I). Then, nucleophilic attack of
barbituric acid enolate to the intermediate (I) gave the
TOF [h−1]c
intermediate (II) which by intramolecular cyclization
148.8
and elimination of water was converted to the
148.8 corresponding spirocyclic product.
150.2 The structure of all products was confirmed by IR, 1H
151.0 NMR, 13C NMR and mass spectroscopy. For example, the
124.3 mass spectrum of 4a demonstrated a molecular ion peak
at m/z: 366, which is according with the proposed struc-
ture. The IR spectrum of 4a displayed absorption band at
3521 cm−1 related to the NH groups, and other strong
absorption bands at 1560,1640 and 1711 cm−1 attributed
8 of 15 KAVYANI AND BAHARFAR

TABLE 3 Synthesis of spirooxindole-dihydropyridine derivatives in the presence of Fe3O4/GO/Au-Aga

a
Reaction conditions: isatins (1 mmol), barbituric acids (1 mmol), 6-amino uracil (0.12 g, 1 mmol), H2O (5 ml), catalyst (20 mg), rt.
b
Reported yield and time.[71]

to C=C and C=O stretching vibrations, respectively. The
1
H-NMR spectrum of 4a in DMSO-d6 exhibited one dou-
blet of doublet at 6.82 ppm (3JHH = 7.6 Hz, 4JHH = 1.2 Hz),
two doublet of triplet at 6.91 ppm (3JHH = 7.2 Hz,
4
JHH = 1.2 Hz) and 7.15 ppm (3JHH = 7.6 Hz,
4
JHH = 1.2 Hz), and one doublet at 6.97 ppm
(3JHH = 7.2 Hz) for aromatic protons. The NH protons
appeared as four singlets at 9.06, 10.60, 11.01 and
11.85 ppm and two other NH groups are displayed as a
broad singlet at 10.45 ppm (Figure 9).
FE3O4/GO/AU-AG CATALYST FOR SYNTHESIS OF SPIROOXINDOLE 9 of 15

SCHEME 2 Proposed mechanism for the three component reaction in the presence of Fe3O4/GO/Au-Ag nanocatalyst

1
FIGURE 9 H-NMR spectrum of 1’H-
spiro[indoline-3,50 -pyrido[2,3-d:6,5-d’]
dipyrimidine]-2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-
pentaone (4a)
10 of 15
F I G U R E 1 1 Reusability tests of Fe3O4/GO/Au-Ag catalyst in
model reaction under optimum conditions
KAVYANI AND BAHARFAR
13
FIGURE 10 C-NMR spectrum of
1’H-spiro[indoline-3,50 -pyrido[2,3-d:6,5-d’]
dipyrimidine]-2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-
pentaone (4a)
The 13C-NMR spectrum of 4a showed 16 distinct reso-
nances that are confirmed the proposed structure. The
most important resonance for spiro carbon appeared at
49.5 ppm (Figure 10).
The synthesized catalyst (Fe3O4/GO/Au-Ag) was sim-
ply removed from the reaction mixture by an external
magnet, therefore its recycle and reusability was investi-
gated in the model reaction. After completion of the reac-
tion, the catalyst retrieved magnetically and washed with
ethyl acetate, dried under vacuum and reused in the next
run. For five cycles (Figure 11) the catalyst could be effi-
ciently recycled and reused without a significant decrease
in product yield. As a result, the heterogeneous catalyst
FIGURE 12 FT-IR spectrum of recovered
Fe3O4/GO/Au-Ag
FE3O4/GO/AU-AG CATALYST FOR SYNTHESIS OF SPIROOXINDOLE
FIGURE 13 XRD pattern of recovered
Fe3O4/GO/Au-Ag
can be reused for at least five cycles without any consid-
erable loss of its catalytic activity.
The structure of the recovered catalyst was character-
ized by FT-IR and XRD analyses. The FT-IR spectrum
clearly indicated that the chemical composition of the
Fe3O4/GO particles did not change significantly during
the reaction process (Figure 12).
Also, the XRD pattern of the recovered catalyst was
very similar to the pattern of the fresh catalyst, which
strongly confirms the stability of the catalyst (Figure 13).
3 | C ON C L U S I ON S
In summary, we have demonstrated a facile and efficient
approach to the preparation of Fe3O4/graphene
oxide/Au-Ag nanocomposite by the layer-by-layer assem-
bly of magnetic ferroferric oxide particles as the core,
graphene oxide nanosheets as a sandwich layer, and Au-
Ag alloy nanoparticles as an external shell. In addition,
the Fe3O4/GO/Au-Ag nanocomposite has been success-
fully employed as a recyclable catalyst for the three-
component synthesis of spirooxindole derivatives with
excellent yields. The catalyst could be easily separated
from the reaction mixture by an external magnet and
reused several times with the minimal loss of catalytic
activity. We believe the Fe3O4/GO/Au-Ag nanocomposite
maybe use as a powerful catalyst for the diversity rang of
organic synthesis.
4 | EXPERIMENTAL SECTION
4.1 | Material and instrumentation
Graphene nanosheets were purchased from Nano USA
Co. All other chemicals were obtained from Fluka,
Merck, and Sigma-Aldrich chemical companies.
Deionized water was obtained by a water purification
11 of 15
system. 1H and 13C-NMR spectra were recorded on a
Bruker DRX-400 AVANCE spectrometer (400.1 and 100.6
respectively) using DMSO-d6 as the solvent. Mass spectra
were recorded on an AGILENT 5975C (USA) mass spec-
trometer. The X-ray diffraction (XRD) patterns were per-
formed on a Philips PW 1730 X-ray diffractometer with
Cu Kα radiation (λ = 1.54 Å) at 40 kV, 30 mA over the 2θ
rang 20 -80 . Thermo-gravimetric analysis (TGA) was
carried out on a BAHR STA 504 analyzer (Germany).
Electron microscopy (TEM) analyses were conducted on
a Zeiss-EM10C-100 kV. Field emission scanning electron
microscope (FE-SEM) experiments were taken using
MIRA3 TESCAN, coupled with an energy-dispersive X-
ray (EDX) analyzer. IR spectra were recorded on a FT-IR
Bruker Vector 22 spectrometer. Melting points were
determined on an Electrothermal 9100 apparat
Transmission.
4.2 | Synthesis of Fe3O4/GO
Firstly, Fe3O4 particles were synthesized by a
solvothermal reaction as reported previously.[72] FeCl3
(2.6 g, 16 mmol), trisodium citrate (0.5 g, 1.7 mmol) and
sodium acetate (4.0 g, 48.8 mmol) were thoroughly dis-
solved in 80 ml of ethylene glycol under magnetic stirring
for 30 min. Then, the mixture was transferred into a
Teflon-lined autoclave and heated at 200  C for 10 h. The
Fe3O4 black particles were collected by an external mag-
net and washed with ethanol and deionized water for
three times, and finally dried in vacuum at 60  C for
12 hr.
0.1 gr of the obtained Fe3O4 was dispersed in ethanol
(80 ml), deionized water (20 ml) and ammonia solution
(1.0 ml) by ultrasonic for 30 min. Then, 0.1 ml of TEOS
and 0.1 ml of APTES were added to the above mixture
and stirring at 40  C for 3 hr. Afterward, the Fe3O4 modi-
fied with APTES (Fe3O4/NH2) was separated and washed
with ethanol and deionized water for three times. The
12 of 15
obtained Fe3O4/NH2 was dispersed in 10 ml deionized
water and mixed with GO (1.0 mg/ml) aqueous solation
(treated with mild ultrasonic) under vigorous stirring at
80  C for 1 hr. Finally, the Fe3O4 particles coated with
GO (Fe3O4/GO) were washed with deionized water for
several times.
4.3 | Preparation of Fe3O4/GO/au-ag
20 ml deionized water dispersion of the obtained Fe3O4/
GO particles was mixed with 2.5 ml 0.01 M HAuCl4.3H2O
aqueous solution and 2.5 ml 0.01 M AgNO3 aqueous solu-
tion under mechanical stirring for 30 min. Then, 10 ml
aqueous solution containing 0.1 M CTAB and 0.01 M
sodium citrate and subsequently 0.1 ml 0.01 M NaOH
were added into the mixture. After stirring at 50  C for
6 hr, the as-prepared Fe3O4/GO/Au-Ag particles were
separated and washed with deionized water for several
times.
4.4 | General procedure for the synthesis
of spirooxindole-dihydropyridine
derivatives
A mixture of isatin derivative (1 mmol), 6-amino uracil
(0.12 g, 1 mmol), barbituric acid derivative (1 mmol) and
20 mg of the catalyst in water (5 ml) was stirred at room
temperature. Completion of the reaction was monitored
by TLC. The catalyst was recovered magnetically from
product solution and washed several times with
ethylacetate which could be used for further reactions.
The solid product was filtered and washed with water
(10 ml) and ethanol (5 ml). The crude product was rec-
rystallized from ethanol to afford the pure product.
4.5 | Spectral data of compounds 4a-l
4.5.1 | 1’H-spiro[indoline-3,50 -pyrido
[2,3-d:6,5-d’]dipyrimidine]-
2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-pentaone (4a)
White powder, m.p.: > 300  C; yield: 90% (330 mg); IR
(KBr) (vmax, cm−1): 3521, 3173, 1711, 1640, 1560, 1493,
1255, 778; 1H NMR (400 MHz, DMSO-d6), δH (ppm): 6.82
(dd, 1H, 3JHH = 7.6 Hz, 4JHH = 1.2 Hz, CHAr), 6.91 (dt,
1H, 3JHH = 7.2 Hz, 4JHH = 1.2 Hz, CHAr), 6.97 (d, 1H,
3
JHH = 7.2 Hz, CHAr), 7.15 (dt, 1H, 3JHH = 7.6 Hz,
4
JHH = 1.2 Hz, CHAr), 9.06 (s, 1H, NH), 10.45 (s, 2H,
2NH), 10.60 (s, 1H, NH), 11.01 (s, 1H, NH), 11.85 (s, 1H,
NH); 13C NMR (100 MHz, DMSO-d6), δC (ppm): 49.5,
KAVYANI AND BAHARFAR
82.6, 97.5, 116.6, 121.6, 123.7, 126.6, 128.5, 135.6, 146.4,
150.4, 151.5, 152.6, 159.0, 162.4, 181.7; MS, m/z:
366 (M+•).
4.5.2 | 8’-Thioxo-80 ,90 -dihydro-1’H-spiro
[indoline-3,50 -pyrido[2,3-d:6,5-d’]
dipyrimidine]-2,20 ,40 ,6’(3’H,7’H,10’H)-
tetraone (4b)
Yellowish powder, m.p.: > 300  C; yield: 91% (348 mg);
IR (KBr) (vmax, cm−1): 3445, 3243, 1717, 1635, 1567, 1493,
1289, 1250, 758; 1H NMR (400 MHz, DMSO-d6), δH
(ppm): 6.85 (d, 1H, 3JHH = 8 Hz, CHAr), 6.93–6.95 (m,
1H, CHAr), 6.96–6.98 (m, 1H, CHAr), 7.18 (t, 1H,
3
JHH = 7.6 Hz, CHAr), 8.84 (s, 1H, NH), 10.50 (s, 1H,
NH), 11.08 (s, 1H, NH), 11.82 (s, 2H, 2NH), 12.08 (s, 1H,
NH); 13C NMR (100 MHz, DMSO-d6), δC (ppm): 49.3,
86.9, 97.0, 116.9, 121.3, 124.2, 126.7, 128.8, 134.9, 145.9,
151.4, 152.7, 159.0, 159.6, 174.0, 181.1; MS, m/z:
382 (M+•).
4.5.3 | 10 ,30 -dimethyl-1’H-spiro[indoline-
3,50 -pyrido[2,3-d:6,5-d’]dipyrimidine]-
2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-pentaone (4c)
White powder, m.p.: > 300  C; yield: 89% (352 mg); IR
(KBr) (vmax, cm−1): 3484, 3266, 3039, 1699, 1623, 1562,
1495, 1400, 1255, 774; 1H NMR (400 MHz, DMSO-d6), δH
(ppm): 3.10 (s, 3H, CH3), 3.44 (s, 3H, CH3), 6.85 (dd, 1H,
3
JHH = 7.6 Hz, 4JHH = 1.2 Hz, CHAr), 6.93–6.97 (m, 1H,
CHAr), 7.18 (dt, 1H, 3JHH = 7.6 Hz, 4JHH = 1.6 Hz, CHAr),
7.25 (d, 1H, 3JHH = 8 Hz, CHAr), 9.31 (s, 1H, NH), 10.48
(s, 1H, NH), 11.04 (s, 1H, NH), 11.92 (s, 1H, NH); 13C
NMR (100 MHz, DMSO-d6), δC (ppm): 27.8, 30.5, 50.3,
83.3, 97.7, 117.2, 121.5, 124.2, 126.3, 128.5, 135.9, 146.3,
150.7, 151.4, 152.7, 159.1, 160.2, 181.7; MS, m/z:
394 (M+•).
4.5.4 | 1-methyl-1’H-spiro[indoline-3,50 -
pyrido[2,3-d:6,5-d’]dipyrimidine]-
2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-pentaone (4d)
White powder, m.p. > 300  C; yield: 90% (343 mg); IR
(KBr) (vmax, cm−1): 3587, 3192, 2852, 1712, 1636, 1526,
1417, 1377, 1233, 754; 1H NMR (400 MHz, DMSO-d6), δH
(ppm): 3.05 (s, 3H, CH3), 6.83 (d, 1H, 3JHH = 7.2 Hz,
CHAr), 6.78–6.80 (m, 1H, CHAr), 7.00 (d, 1H, 3JHH = 7.2 Hz,
CHAr), 7.11 (d, 1H, 3JHH = 7.4 Hz, CHAr), 10.62 (s, 3H,
3NH), 11.15 (s, 2H, 2NH); 13C NMR (100 MHz, DMSO-
d6), δC (ppm): 26.8, 51.3, 88.8, 107.3, 108.8, 122.6, 124.3,
FE3O4/GO/AU-AG CATALYST FOR SYNTHESIS OF SPIROOXINDOLE
127.9, 129.3, 134.9, 144.3, 145.0, 150.0, 150.6, 161.5, 174.7,
178.1; MS, m/z: 380 (M+•).
4.5.5 | 5-Chloro-1’H-spiro[indoline-3,50 -
pyrido[2,3-d:6,5-d’]dipyrimidine]-
2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-pentaone (4e)
White powder, m.p.: > 300  C; yield: 92% (369 mg); IR
(KBr) (vmax, cm−1): 3488, 3179, 1712, 1636, 1559, 1460,
1246, 1098, 818; 1H NMR (400 MHz, DMSO-d6), δH
(ppm): 6.80 (d, 1H, 4JHH = 2 Hz, CHAr), 7.05 (d, 1H,
3
JHH = 8.4 Hz, CHAr), 7.22 (dd, 1H, 3JHH = 8.8 Hz,
4
JHH = 2 Hz, CHAr), 9.29 (s, 1H, NH), 10.50 (s, 2H, 2NH),
10.66 (s, 2H, 2NH), 11.06 (s, 1H, NH), 11.90 (s, 1H, NH);
13
C NMR (100 MHz, DMSO-d6), δC (ppm): 49.5, 82.5,
97.1, 118.5, 123.5, 126.1, 127.0, 128.6, 134.9, 146.3, 150.4,
151.6, 152.9, 159.1, 162.3, 181.3; MS, m/z: 400 (M+•).
4.5.6 | 5-Chloro-80 -thioxo-80 ,90 -dihydro-
1’H-spiro[indoline-3,50 -pyrido[2,3-d:6,5-d’]
dipyrimidine]-2,20 ,40 ,6’(3’H,7’H,10’H)-
tetraone (4f)
White powder, m.p.: > 300  C; yield: 93% (388 mg); IR
(KBr) (vmax, cm−1): 3517, 3250, 1719, 1682, 1645, 1560,
1492, 1389, 1281, 1099, 831; 1H NMR (400 MHz, DMSO-
d6), δH (ppm): 6.85 (d, 1H, 4JHH = 2.4 Hz, CHAr), 7.05 (d,
1H, 3JHH = 8.8 Hz, CHAr), 7.25 (dd, 1H, 3JHH = 8.4 Hz,
4
JHH = 2.4 Hz, CHAr), 9.01(s, 1H, NH), 10.56 (s, 1H, NH),
11.17 (s, 1H, NH), 11.97 (s, 2H, 2NH), 12.16 (s, 1H, NH);
13
C NMR (100 MHz, DMSO-d6), δC (ppm): 49.3, 86.8,
96.6, 118.9, 123.2, 126.2, 127.5, 128.8, 134.1, 145.7, 151.4,
153.1, 159.1, 159.5, 174.1, 180.7; MS, m/z: 416 (M+•).
4.5.7 | 5-chloro-10 ,30 -dimethyl-1’H-spiro
[indoline-3,50 -pyrido[2,3-d:6,5-d’]
dipyrimidine]-2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-
pentaone (4 g)
White powder, m.p.: > 300  C; yield: 90% (387 mg); IR
(KBr) (vmax, cm−1): 3451, 3063, 2923, 1706, 1661, 1630,
1535, 1486, 1398, 1250, 1099, 821; 1H NMR (400 MHz,
DMSO-d6), δH (ppm): 3.09 (s, 3H, CH3), 3.41 (s, 3H,
CH3), 6.84 (d, 1H, 4JHH = 2 Hz, CHAr), 7.05 (d, 1H,
3
JHH = 8 Hz, CHAr), 7.24–7.27 (m, 1H, CHAr), 9.45(s, 1H,
NH), 10.52 (s, 1H, NH), 11.09 (s, 1H, NH), 11.93 (s, 1H,
NH); 13C NMR (100 MHz, DMSO-d6), δC (ppm): 27.9,
30.5, 50.3, 83.2, 97.3, 119.1, 123.5, 127.1, 127.6, 128.7,
135.1, 146.1, 150.7, 151.4, 159.1, 160.1, 162.3, 181.3; MS,
m/z: 428 (M+•).
13 of 15
4.5.8 | 1-benzyl-1’H-spiro[indoline-3,50 -
pyrido[2,3-d:6,5-d’]dipyrimidine]-
2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-pentaone (4 h)
White powder, m.p.: > 300  C; yield: 81% (372 mg); IR
(KBr) (vmax, cm−1): 3436, 3201, 3085, 2856, 1712, 1612,
1530, 1423, 1253, 764, 698; 1H NMR (400 MHz, DMSO-
d6), δH (ppm): 5.22 (s, 2H, CH2), 6.61 (d, 1H, 3JHH = 7.6 Hz,
CHAr), 6.97–6.99 (m, 1H, CHAr), 7.12–7.14 (m, 1H, CHAr),
7.21–7.22 (m, 1H, CHAr), 7.27–7.28 (m, 1H, CHAr),
7.33–7.34 (m, 4H, 4CHAr), 11.25 (s, 5H, 5NH); 13C NMR
(100 MHz, DMSO-d6), δC (ppm): 44.2, 53.3, 74.6, 88.5,
109.5, 122.7, 124.5, 127.5, 128.0, 128.6, 129.1, 129.2, 136.3,
144.2, 144.4, 149.8, 150.6, 151.4, 155.5, 161.7, 164.7, 168.2,
174.9; MS, m/z: 456 (M+•).
4.5.9 | 1-Benzyl-80 -thioxo-80 ,90 -dihydro-
1’H-spiro[indoline-3,50 -pyrido[2,3-d:6,5-d’]
dipyrimidine]-2,20 ,40 ,6’(3’H,7’H,10’H)-
tetraone (4i)
White powder, m.p.: > 300  C; yield: 84% (398 mg); IR
(KBr) (vmax, cm−1): 3447, 3189, 3057, 2923, 1689, 1610,
1534, 1439, 1378, 1301, 756, 698; 1H NMR (400 MHz,
DMSO-d6), δH (ppm): 4.77–4.91 (m, 2H, CH2), 6.41–6.45
(m, 1H, CHAr), 6.82–6.87 (m, 1H, CHAr), 6.99–7.05 (m,
1H, CHAr), 7.07–7.14 (m, 1H, CHAr), 7.24–7.30 (m, 3H,
3CHAr), 7.60 (d, 2H, 3JHH = 7.2 Hz, 2CHAr), 9.05 (s, 1H,
NH), 10.86 (m, 2H, 2NH), 11.75 (s, 1H, NH), 12.24 (s,
1H, NH); 13C NMR (100 MHz, DMSO-d6), δC (ppm):
44.5, 56.5, 88.5, 93.1, 108.1, 122.1, 123.6, 127.2, 127.5,
128.1, 128.6, 134.5, 137.3, 137.4, 144.4, 144.6, 149.9,
150.1, 159.1, 161.8, 162.7, 173.9, 178.0; MS, m/z:
472 (M+•).
4.5.10 | 1-(prop-2-yn-1-yl)-1’H-spiro
[indoline-3,50 -pyrido[2,3-d:6,5-d’]
dipyrimidine]-2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-
pentaone (4j)
Pinkish powder, m.p.: 300  C decomposed; yield: 86%
(348 mg); IR (KBr) (vmax, cm−1): 3454, 3273, 3193, 2925,
1725, 1690, 1611, 1526, 1489, 1441, 1300, 760; 1H NMR
(400 MHz, DMSO-d6), δH (ppm): 3.14–3.15 (t, 1H,
4
JHH = 2.4 Hz, CH), 4.40–4.41 (d, 2H, 4JHH = 2.4 Hz,
CH2), 6.87–6.93 (m, 2H, 2CHAr), 7.06 (d, 1H, 3JHH = 6.4 Hz,
CHAr), 7.17 (dt, 1H, 3JHH = 7.6 Hz, 4JHH = 1.2 Hz, CHAr),
8.69 (s, 1H, NH), 10.75 (s, 2H, 2NH), 11.30 (s, 2H, 2NH),;
13
C NMR (100 MHz, DMSO-d6), δC (ppm): 29.7, 46.9,
74.4, 78.6, 88.6, 108.0, 122.1, 123.4,128.0,134.7, 143.6,
144.3, 150.0, 161.5, 177.1; MS, m/z: 404 (M+•).
14 of 15
4.5.11 | 1-(Prop-2-yn-1-yl)-80 -thioxo-80 ,90 -
dihydro-1’H-spiro[indoline-3,50 -pyrido
[2,3-d:6,5-d’]dipyrimidine]-
2,20 ,40 ,6’(3’H,7’H,10’H)-tetraone (4 k)
Pinkish powder, m.p.: 260  C decomposed; yield: 88%
(371 mg); IR (KBr) (vmax, cm−1): 3426, 3290, 3159, 2963,
1677, 1610, 1529, 1492, 1464, 1370, 1260, 757; 1H NMR
(400 MHz, DMSO-d6), δH (ppm): 3.16–3.17 (m, 1H, CH),
4.39–4.40 (m, 2H, CH2), 6.85–6.92 (m, 2H, 2CHAr), 7.05
(d, 1H, 3JHH = 7.2 Hz, CHAr), 7.16 (t, 1H, 3JHH = 7.6 Hz,
CHAr), 10.63 (s, 3H, 3NH), 11.83 (s, 2H, 2NH); 13C NMR
(100 MHz, DMSO-d6), δC (ppm): 29.7, 48.2, 74.4, 78.6,
88.3, 107.8, 114.1, 121.1, 122.1, 123.5, 127.8, 135.4, 143.5,
146.1, 150.1, 159.1, 161.6, 174.2, 185.1; MS, m/z:
420 (M+•).
4.5.12 | 10 ,30 -dimethyl-1-(prop-2-yn-1-yl)-
1’H-spiro[indoline-3,50 -pyrido[2,3-d:6,5-d’]
dipyrimidine]-2,20 ,40 ,60 ,8’(3’H,7’H,9’H,10’H)-
pentaone (4 l)
Pinkish powder, m.p.: 300  C decomposed; yield: 83%
(360 mg); IR (KBr) (vmax, cm−1): 3433, 3294, 2962, 2858,
1723, 1677, 1526, 1444, 1425, 1375, 1270, 752; 1H NMR
(400 MHz, DMSO-d6), δH (ppm): 3.00 (s, 3H, CH3), 3.05
(s, 3H, CH3), 3.31–3.32 (m, 1H, CH), 4.42 (s, 2H, CH2),
6.99–7.04 (m, 2H, 2CHAr), 7.28–7.32 (m, 2H, 2CHAr), 8.57
(s, 1H, NH), 10.76 (s, 1H, NH), 11.27 (s, 1H, NH); 13C
NMR (100 MHz, DMSO-d6), δC (ppm): 28.7, 28.9, 29.5,
52.2, 75.0, 78.1, 88.6, 108.0, 109.4, 123.1, 125.5, 129.6,
134.7, 143.1, 144.2, 150.0, 151.5, 161.5, 166.1, 173.5, 177.1;
MS, m/z: 432 (M+•).
A C K N O WL E D G M E N T S
The authors would like to thank the Research Council of
Mazandaran University for financial support.
ORCID
Robabeh Baharfar https://orcid.org/0000-0002-8215-
1851
R EF E RE N C E S
[1] O. L. Muskens, N. Del Fatti, F. Vallée, J. R. Huntzinger,
P. Billaud, M. Broyer, Appl. Phys. Lett. 2006, 88. 063109
[2] M. Kidwai, V. Bansal, A. Kumar, S. Mozumdar, Green Chem.
2007, 9, 742.
[3] E. C. Dreaden, A. M. Alkilany, X. Huang, C. J. Murphy,
M. A. El-Sayed, Chem. Soc. Rev. 2012, 41, 2740.
[4] L. Olofsson, T. Rindzevicius, I. Pfeiffer, M. Käll, F. Höök,
Langmuir 2003, 19, 10414.
KAVYANI AND BAHARFAR
[5] S. U. Son, Y. Jang, J. Park, H. B. Na, H. M. Park, H. J. Yun,
T. Hyeon, J. Am. Chem. Soc. 2004, 126, 5026.
[6] M. O. Nutt, J. B. Hughes, M. S. Wong, Environ. Sci. Technol.
2005, 39, 1346.
[7] S. T. Christensen, H. Feng, J. L. Libera, N. Guo, J. T. Miller,
P. C. Stair, J. W. Elam, Nano Lett. 2010, 10, 3047.
[8] J. Y. Park, Y. Zhang, M. Grass, T. Zhang, G. A. Somorjai, Nano
Lett. 2008, 8, 673.
[9] M. A. Schmidt, L. P. Sempere, H. K. Tyagi, C. G. Poulton,
P. S. J. Russell, Phys. Rev. B 2008, 77. 033417
[10] X. Y. Dong, Z. W. Gao, K. F. Yang, W. Q. Zhang, L. W. Xu,
Catal. Sci. Technol. 2015, 5, 2554.
[11] L. Shang, S. Dong, G. U. Nienhaus, Nano Today 2011, 6, 401.
[12] K. S. Lee, M. A. El-Sayed, J. Phys. Chem. B 2006, 110, 19220.
[13] C. Li, L. Sun, Y. Sun, T. Teranishi, Chem. Mater. 2013, 25,
2580.
[14] C. G. Khoury, T. Vo-Dinh, J. Phys. Chem. C 2008, 112, 18849.
[15] A. Q. Wang, C. M. Chang, C. Y. Mou, J. Phys. Chem. B 2005,
109, 18860.
[16] A. Q. Wang, J. H. Liu, S. D. Lin, T. S. Lin, C. Y. Mou, J. Catal.
2005, 233, 186.
[17] J. H. Liu, A. Q. Wang, Y. S. Chi, H. P. Lin, C. Y. Mou, J. Phys.
Chem. B 2005, 109, 40.
[18] X. Liu, A. Wang, T. Zhang, D. S. Su, C. Y. Mou, Catal. Today
2011, 160, 103.
[19] W. Li, L. Kuai, Q. Qin, B. Geng, J. Mater. Chem. A 2013, 1,
7111.
[20] G. C. Papavassiliou, J. Phys. F 1976, 6, L103.
[21] Y. Sun, Y. Xia, J. Am. Chem. Soc. 2004, 126, 3892.
[22] B. Neppolian, C. Wang, M. Ashokkumar, Ultrason. Sonochem.
2014, 21, 1948.
[23] Y. Shin, I. T. Bae, B. W. Arey, G. J. Exarhos, J. Phys. Chem. C
2008, 112, 4844.
[24] X. Liu, A. Wang, L. Li, T. Zhang, C. Y. Mou, J. F. Lee, Prog.
Nat. Sci.: Mater. Int. 2013, 23, 317.
[25] S. Anandan, F. Grieser, M. Ashokkumar, J. Phys. Chem. C
2008, 112, 15102.
[26] H. L. Jiang, T. Akita, T. Ishida, M. Haruta, Q. Xu, J. am.Chem.
Soc. 2011, 133, 1304.
[27] A. Pandikumar, S. Manonmani, R. Ramaraj, Catal. Sci.
Technol. 2012, 2, 345.
[28] S. Tang, S. Vongehr, X. Meng, J. Mater. Chem. 2010, 20, 5436.
[29] M. J. Allen, V. C. Tung, R. B. Kaner, Chem. Rev. 2009,
110, 132.
[30] W. Choi, I. Lahiri, R. Seelaboyina, Y. S. Kang, Crit. Rev. Solid
State Mater. Sci. 2010, 35, 52.
[31] D. R. Dreyer, S. Park, C. W. Bielawski, R. S. Ruoff, Chem. Soc.
Rev. 2010, 39, 228.
[32] J. Song, L. Xu, R. Xing, Q. Li, C. Zhou, D. Liu, H. Song, Sci.
Rep. 2014, 4, 7515.
[33] G. Wang, W. Feng, X. Zeng, Z. Wang, C. Feng,
D. T. McCarthy, X. Zhang, Water Res. 2016, 94, 363.
[34] B. Li, T. Liu, Y. Wang, Z. Wang, J. Colloid Interface Sci. 2012,
377, 114.
 Mastalir, Z. Király, A. Patzko, I. Dékány, P. L'Argentiere,
[35] A.
Carbon 2008, 46, 1631.
[36] Y. Li, Y. Cao, J. Xie, D. Jia, H. Qin, Z. Liang, Cat. Com. 2015,
58, 21.
FE3O4/GO/AU-AG CATALYST FOR SYNTHESIS OF SPIROOXINDOLE
[37] Y. Liu, P. She, J. Gong, W. Wu, S. Xu, J. Li, A. Deng, Sens.
Actuators B 2015, 221, 1542.
[38] Y. He, N. Zhang, L. Zhang, Q. Gong, M. Yi, W. Wang, J. Gao,
Mater. Res. Bull. 2014, 51, 397.
[39] S. G. Babu, M. Gopiraman, D. Deng, K. Wei, R. Karvembu,
I. S. Kim, Chem. Eng. J. 2016, 300, 146.
[40] T. Wu, J. Ma, X. Wang, Y. Liu, H. Xu, J. Gao, J. Yan, Nano-
technology 2013, 24. 125301
[41] F. Liu, F. Niu, N. Peng, Y. Su, Y. Yang, RSC Adv. 2015, 5,
18128.
[42] F. H. Lin, R. A. Doong, J. Phys. Chem. C 2011, 115, 6591.
[43] X. Yang, W. Chen, J. Huang, Y. Zhou, Y. Zhu, C. Li, Sci. Rep.
2015, 5, 10632.
[44] J. Xu, C. Wang, Z. Rong, X. A. Cheng, R. Xiao, RSC Adv. 2015,
5, 62101.
[45] K. Liang, X. Li, S. Z. Kang, L. Qin, G. Li, J. Mu, Carbon 2014,
80, 716.
[46] H. Singh, J. Sindhu, J. M. Khurana, C. Sharma, K. R. Aneja,
Eur. J. Med. Chem. 2014, 77, 145.
[47] N. Ye, H. Chen, E. A. Wold, P. Y. Shi, J. Zhou, ACS Infect. Dis.
2016, 2, 382.
[48] B. Yu, D. Q. Yu, H. M. Liu, Eur. J. Med. Chem. 2015, 97, 673.
[49] J. B. Mitchell, A. Russo, J. A. Cook, K. L. Straus, E. Glatstein,
Int. J. Radiat. Biol. 1989, 56, 827.
[50] M. Schramm, R. Towart, B. Lamp, G. Thomas, J. Cardiovasc.
Pharmacol. 1985, 7, 493.
[51] T. Shibanuma, M. Iwanani, K. Okuda, T. Takenaka,
M. Murakami, Chem. Pharm. Bull. 1980, 28, 2809.
[52] O. Andersson, C. Bengtsson, D. Elmfeldt, K. Haglund,
T. Hedner, P. Seideman, J. Ostman, Br. J. Clin. Pharmacol.
1984, 17, 257.
[53] R. C. Cioc, E. Ruijter, R. V. Orru, Green Chem. 2014, 16, 2958.
[54] A. Domling, W. Wang, K. Wang, Chem. Rev. 2012, 112, 3083.
[55] I. Ugi, A. Dömling, W. Hörl, Endeavour 1994, 18, 115.
[56] J. M. Khurana, A. Chaudhary, B. Nand, A. Lumb, Tetrahedron
Lett. 2012, 53, 3018.
[57] A. Dandia, V. Parewa, A. K. Jain, K. S. Rathore, Green Chem.
2011, 13, 2135.
[58] M. Nasrollahzadeh, Z. Issaabadi, S. M. Sajadi, RSC Adv. 2018,
8, 27631.
15 of 15
[59] S. M. Sajadi, K. Kolo, M. Pirouei, S. A. Mahmud, J. A. Ali,
S. M. Hamad, RSC Adv. 2018, 8, 35557.
[60] M. Sajjadi, M. Nasrollahzadeh, S. M. Sajadi, J. Colloid Interface
Sci. 2017, 497, 1.
[61] R. Baharfar, S. Mohajer, Catal. Lett. 2016, 146, 1729.
[62] N. Porahmad, R. Baharfar, Res. Chem. Intermed. 2018, 44, 305.
[63] R. Baharfar, N. Shariati, C. R. Chim. 2014, 17, 413.
[64] K. Jadidi, R. Ghahremanzadeh, A. Bazgir, J. Comb. Chem.
2009, 11, 341.
[65] S. Karamthulla, S. Pal, M. N. Khan, L. H. Choudhury, RSC
Adv. 2013, 3, 15576.
[66] R. Ghahremanzadeh, M. Sayyafi, S. Ahadi, A. Bazgir, J. Comb.
Chem. 2009, 11, 393.
[67] B. Liang, S. Kalidindi, J. A. Porco Jr., C. R. Stephenson, Org.
Lett. 2010, 12, 572.
[68] M. Nasrollahzadeh, M. Atarod, S. M. Sajadi, J. Colloid Interface
Sci. 2017, 486, 153.
[69] M. Maham, M. Nasrollahzadeh, S. M. Sajadi, M. Nekoei,
J. Colloid Interface Sci. 2017, 497, 33.
[70] M. Atarod, M. Nasrollahzadeh, S. M. Sajadi, J. Colloid Interface
Sci. 2016, 465, 249.
[71] A. Khalafi-Nezhad, S. Mohammadi, ACS Comb. Sci. 2013,
15, 512.
[72] Y. Deng, Y. Cai, Z. Sun, J. Liu, C. Liu, J. Wei, W. Li, C. Liu,
Y. Wang, D. Zhao, J. Am. Chem. Soc. 2010, 132, 8466.
SU PP O R TI N G I N F O RMA TI O N
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How to cite this article: Kavyani S, Baharfar R.
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