Applied Surface Science Advances 5 (2021) 100096

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Applied Surface Science Advances

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Magnetic nanoporous MCM-41 supported melamine: A powerful

nanocatalyst for synthesis of biologically active 2-amino-3-cyanopyridines
Zahra Haydari, Dawood Elhamifar∗, Masoumeh Shaker, Meysam Norouzi
Department of Chemistry, Yasouj University, Yasouj, 75918-74831, Iran

a r t i c l e i n f o a b s t r a c t

Keywords: A novel core-shell structured magnetic nanocomposite supported melamine with mesoporous silica shell and mag-
Magnetite nanocomposite netite core (Fe3 O4 @MCM-41/Melamine) was synthesized and used as powerful nano-organocatalyst for prepa-
Core–shell ration of 2-amino-3-cyanopyridines. The Fe3 O4 @MCM-41/Melamine was synthesized via chemical grafting of
Supported melamine
propylmelamine groups on Fe3 O4 @MCM-41 nanocomposite. The structural and chemical characteristics of the
2-amino-3-cyanopyridines
Fe3 O4 @MCM-41/Melamine were studied using Fourier transform infrared (FT-IR) spectroscopy, vibrating sam-
Ultrasonic conditions
ple magnetometer (VSM), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and energy-
dispersive X-ray (EDX) techniques. The Fe3 O4 @MCM-41/Melamine was used as powerful catalyst for preparation
of 2-amino-3-cyanopyridines in water. This nanocatalyst was magnetically recovered and reused several times
with keeping its efficiency.

1. Introduction of their magnetic properties [17,18]. In order to solve these problems

Heterocycles are among biologically active organic compounds [1].
Particularly, the pyridine containing heterocycles are more attractive
due to their widespread chemical and pharmaceutical applications
[2,3]. As example, 2-amino-3-cyanopyridines have been used as IKK-
b inhibitor and A2Aadenosine receptor antagonist [4–6]. To date, sev-
eral strategies have been reported for the production of 2-amino-3-
cyanopyridines. However, the most of these methods suffer from restric-
tions of high temperature, long reaction time and low yield [7]. Given
these circumstances, an efficient design of a recyclable and environmen-
tally friendly catalyst working in mild conditions is still an important
challenge in the production of 2-amino-3-cyanopyridines.
On the other hand, the core-shell microspheres containing a mag-
netic metallic oxide core play an important role in chemistry, physics
and material sciences. These materials are used to provide microelec-
tronic circuits, sensors, fuel cells and catalysts [8,9]. Among different
kinds of metallic oxides, magnetite nanoparticles are particularly
important due to their easy preparation, biological compatibility,
high special surface and easy separation by external magnetic fields
[10–13]. These NPs have diverse applications in the fields of catalysis,
medicine such as pharmaceuticals and magnetic resonance imaging,
adsorption and separation technologies [14–16]. Despite the vast ap-
plications of these super paramagnetic NPs in chemical and biomedical
processes, their inherent disadvantages such as self-assembly and
accumulation in acidic environments and oxidation in air lead to loss
and keep the properties of these particles on nanoscale, they are
coated with a special layer of organic material such as polymer or
an inorganic layer of silica, carbon and metal oxides 19–22]. Among
these, silica coatings are most suitable due to low toxicity, high avail-
ability, high surface area, good thermal and biological stability, easy
functionalization with organic and inorganic catalysts, low reactivity
and ineffectiveness in acidic media [23,24]. Especially, magnetic
mesoporous silicas with core–shell structure, due to their hierarchical
porous arrangement, excellent surface area and high selectivity, are
very attractive in this matter. These have been employed as useful
and versatile solid support for homogeneous catalysts in different
chemical transformations [25,26]. Some recently developed examples
are Fe3 O4 @MCM‐41@Zr‐piperazine‐MNPs [27], Fe3 O4 @mesoporous
SBA-15 [28], Fe3 O4 @NH2 -mesoporous silica@Polypyrrole/Pd [29],
Fe3 O4 @MCM-41/ZnBr2 [30], Fe3 O4 @FeSO4 − MCM-41 [31] and
Fe3 O4 /MCM-41 composite supported sodium silicate [32].
In view of the above and in following of our previous stud-
ies [33–35], herein, a novel magnetite mesoporous nanocomposite
functionalized with melamine (Fe3 O4 @MCM-41/Melamine) is syn-
thesized and applied as powerful nanocatalyst for production of 2-
amino-3-cyanopyridines. The melamine was selected as an impor-
tant organic group for functionalization of our designed nanocom-
posite due to it is a strong base for a variety of base-catalyzed or-
ganic reactions [36–38] as well as its easy chemical immobilization on
Fe3 O4 @MCM-41.

∗
Corresponding author.
E-mail address: d.elhamifar@yu.ac.ir (D. Elhamifar).

https://doi.org/10.1016/j.apsadv.2021.100096
Received 3 December 2020; Received in revised form 18 March 2021; Accepted 18 March 2021
2666-5239/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
Z. Haydari, D. Elhamifar, M. Shaker et al.
Scheme 1. Preparation of Fe3 O4 @MCM-41/Melamine.
2. Experimental
2.1. Preparation of Fe3 O4 @MCM-41
To do this, firstly Fe3 O4 @SiO2 nanoparticles were synthesized ac-
cording to known procedures [39,40]. Then, Fe3 O4 @SiO2 NPs (1 g)
were dispersed in deionized H2 O (80 mL) and EtOH (60 mL) at 40 °C un-
der ultrasonic waves for 30 min. After that, NH3 (25% wt, 3.5 mL) and
cetyltrimethylammonium bromide (CTAB) surfactant (1 g) were added
and this was stirred at RT for 10 min. Subsequently, tetramethoxysilane
(TMOS, 0.5 mL) was added drop-wise and stirring was first continued
at RT for 2 h and then at 100 °C for 48 h. The resulted material was
collected by using an external magnet and washed with deionized H2 O
(50 mL) and EtOH (50 mL). The CTAB surfactant was removed after
calcination of resulting solid for 6 h at 500 °C. The final magnetic meso-
porous material was called Fe3 O4 @MCM-41.
2.2. Preparation of Fe3 O4 @MCM-41/melamine
For the preparation of Fe3 O4 @MCM-41/Melamine, firstly,
Fe3 O4 @MCM-41 NPs (0.5 g) were added in dry toluene (25 mL)
and well dispersed under ultrasonic irradiations. After 30 min, 0.25 mL
of 3-(chloropropyl)trimethoxysilane was added and the mixture was re-
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Applied Surface Science Advances 5 (2021) 100096
fluxed for 24 h under argon atmosphere. The product was magnetically
collected and washed thoroughly with dry EtOH (50 mL) to remove
unreacted 3-(chloropropyl)trimethoxysilane. This was dried at 75 °C for
4 h and called Fe3 O4 @MCM-41@Pr-Cl. Next, Fe3 O4 @MCM-41/Pr-Cl
microspheres (0.6 g), melamine (0.3 g) and triethylamine (0.01 g)
were added in toluene (25 mL) and refluxed for 24 h. Finally, the
product was collected by using an external magnet, washed with
EtOH (80 mL), dried at 70 °C for 8 h and named Fe3 O4 @MCM-41/
Melamine.
2.3. Procedure for the synthesis of 2-amino-3-cyanopyridines
In order to synthesis 2-amino-3-cyanopyridines, typically, acetophe-
none (1 mmol), aldehyde (1 mmol), malononitrile (1 mmol), ammo-
nium acetate (1 mmol) and Fe3 O4 @MCM-41/Melamine catalyst (10 mg,
0.41 mol%) were added into a flask containing H2 O (3 mL). The resulted
mixture was placed in an ultrasonic bath at 50 °C. After finishing of the
reaction, hot EtOH (10 mL) was added and Fe3 O4 @MCM-41/Melamine
was magnetically separated. Next, some ice species were added into fil-
trate to precipitate or crystallize of desired crude products. At the end,
the pure 2-amino-3-cyanopyridines were obtained after recrystallization
of crude mixture in EtOH.
Z. Haydari, D. Elhamifar, M. Shaker et al.
Fig. 1. FT-IR spectra of a) Fe3 O4 @MCM-41/CTAB, b) Fe3 O4 @MCM-41 and c)
Fe3 O4 @MCM-41/Melamine.
3. Results and discussion
The synthesis procedure of Fe3 O4 @MCM-41@Melamine micro-
sphere is shown in Scheme 1. Briefly, the whole procedure involves fol-
lowing steps: 1) magnetite NPs were synthesized via a co-precipitation
approach and modified by silica in order to provide core-shell struc-
tured Fe3 O4 @SiO2 , 2) CTAB was selected as surfactant for the mod-
ification of Fe3 O4 @SiO2 with a mesoporous silica shell and forma-
tion of Fe3 O4 @MCM-41, 3) the Fe3 O4 @MCM-41 was reacted with first
3-(chloropropyl)trimethoxysilane and then melamine to prepare the
Fe3 O4 @MCM-41/Melamine nanocatalyst (Scheme 1). It should be noted
that in the last step, the chloride ion of Fe3 O4 @MCM-41/Pr-Cl nanocom-
Fig. 2. EDX analysis of the Fe3 O4 @MCM-41/Melamine.
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Applied Surface Science Advances 5 (2021) 100096
posite is replaced with melamine through a SN 2 reaction to for final
material. Due to presence of melamine, the designed Fe3 O4 @MCM-
41/Melamine acts as a powerful base catalyst for different organic re-
actions. In the present study, the Fe3 O4 @MCM-41/Melamine was used
as efficient, easy recoverable and durable nanocatalyst in the synthesis
of biologically active 2-amino-3-cyanopyridines.
The FT-IR analysis of Fe3 O4 @MCM-41/CTAB, Fe3 O4 @MCM-41 and
Fe3 O4 @MCM-41/Melamine nanomaterials is demonstrated in Fig. 1.
The Fe–O and O–H bonds are seen, respectively, at 568 and 3400 cm−1
for all samples. The bands cleared at 1080, 1135 and 960 cm−1 are as-
signed to vibrations of Si–O–Si bonds. For Fe3 O4 @MCM-41/CTAB, the
sharp peaks at 2850 and 2920 cm−1 are attributed to C–H vibrations of
CTAB moieties (Fig. 1a). Interestingly, for Fe3 O4 @MCM-41, the latter
peaks are not seen indicating well elimination of CTAB during calcina-
tion (Fig. 1b). For Fe3 O4 @MCM-41/Melamine (Fig. 1c), the peaks at
3415–3471, 1630 and 1560 cm −1 are, respectively, attributed to vibra-
tions of N–H, C = N and C–N bonds of melamine rings. These confirm
high stability of magnetite cores, successful coating of mesoporous silica
shell around MNPs and well immobilization of melamine groups.
The EDX spectrum showed the signals of C, Si, Fe, O, and N elements.
The presence of these signals confirms the successful immobilization of
melamine groups on the magnetic mesoporous nanoparticles (Fig. 2).
The magnetic properties of the catalyst were measured by using VSM.
Based on this analysis, a saturation magnetization of about 10.8 emu/g
was found for the Fe3 O4 @MCM-41/Melamine. The amount of magnetic
saturation of the catalyst is lower than that of Fe3 O4 NPs confirming
well modification of magnetite NPs with mesoporous silica shell and
melamine groups (Fig. 3) [41]. It is important to note, this nanocatalyst
was easily collected using a magnetic field during both preparation and
catalytic processes (inset of Fig. 3).
The powder X-ray diffraction (PXRD) analysis of Fe3 O4 @MCM-
41/Melamine showed six peaks at 2𝜃 =13.0, 17.6, 22.2, 26.5, 28.9
and 29.8° that is in good agreement with the standard PXRD pat-
tern of melamine containing materials [42]. This analysis also showed
six peaks at 2𝜃 = 30.2, 35.5, 43.2, 54.1, 57.2 and 62.5° correspond-
ing to magnetite NPs [41,42]. These data confirm successful immobi-
lization of melamine moieties on the material surface and also prove
Z. Haydari, D. Elhamifar, M. Shaker et al. Applied Surface Science Advances 5 (2021) 100096

Fig. 3. VSM analysis of the Fe3 O4 @MCM-41/Melamine.

Table 1
The effect of solvent, temperature and catalyst loading in the synthesis of 2-amino-3-cyanopyridinesa .

Entry Catalyst Catalyst (mg) [mol%] Time (min) T ( °C) Solvent Yield (%)b

1 — — 60 50 H2 O Trace
2 Fe3 O4 @MCM-41/Melamine 5 [0.20] 20 50 H2 O 28
3c Fe3 O4 @MCM-41/Melamine 10 [0.41] 20 50 H2 O 95
4 Fe3 O4 @MCM-41/Melamine 15 [0.62] 20 50 H2 O 95
5 Fe3 O4 @MCM-41/Melamine 10 [0.41] 20 25 H2 O 60
6 Fe3 O4 @MCM-41/Melamine 10 [0.41] 20 65 H2 O 95
7 Fe3 O4 @MCM-41/Melamine 10 [0.41] 20 50 CH3 CN 47
8 Fe3 O4 @MCM-41/Melamine 10 [0.41] 20 50 EtOH 88
9 Fe3 O4 @MCM-41/Melamine 10 [0.41] 20 50 Toluene 38
10 Fe3 O4 @MCM-41 10 [0.41] 20 50 H2 O Trace
a
Conditions: Acetophenone (1 mmol), benzaldehyde (1 mmol), malononitrile (1 mmol), ammonium acetate
(1 mmol) and solvent (3 mL).
b
Isolated yields.
c
Optimum conditions.

high stability of magnetite NPs during the modification processes
(Fig. 4).
In order to determine the shape and surface morphology of the
Fe3 O4 @MCM-41/Melamine, the SEM analysis was performed. The SEM
image showed that the Fe3 O4 @MCM-41/Melamine nanocomposite has
spherical particles with an average size of 60 nm (Fig. 5). These type
particles are very important and attractive in the fields of chromatogra-
phy, catalysis and adsorption.
After successful characterization, the catalytic application of
Fe3 O4 @MCM-41/Melamine nanocatalyst was studied in the production
of 2-amino-3-cyanopyridines. To optimize the conditions, the condensa-
tion of benzaldehyde, acetophenone, ammonium acetate and malonon-
itrile was used as a model reaction (Table 1). Firstly, the model reaction
was performed in the absence of the Fe3 O4 @MCM-41/Melamine under
ultrasonic conditions in which no product was obtained (Table 1, en-
try 1). Then, different amounts of catalyst were added in the reaction
mixture and the progress was monitored under ultrasonic irradiations
(Table 1, entries 2–4). It was found that using 10 mg (0.41 mol%) of
catalyst gives the best yield of desired product (Table 1, entry 3). Also,
the temperature effect showed that at 50 °C the highest conversion is
resulted (Table 1, entries 3, 5 and 6). Among different solvents, the
best result was obtained in water under ultrasonic conditions that is
an advantage of the present catalytic system based on green chemistry
and environmental principles. In order to investigate the neat effect of
melamine groups, in another experiment the understudied process was
conducted in the presence of melamine-free Fe3 O4 @MCM-41 nanocom-

4
Z. Haydari, D. Elhamifar, M. Shaker et al.
Fig. 4. PXRD analysis of Fe3 O4 @MCM-41/Melamine.
Fig. 5. SEM image of the Fe3 O4 @MCM-41/Melamine.
posite. Interestingly, no product was obtained after 60 min (Table 1, en-
try 10) confirming that the main process is performed using melamine
groups.
Using the best reaction conditions, the activity of the de-
signed nanocatalyst, for synthesis different derivatives of 2-amino-3-
cyanopyridines, was further studied by using various aldehydes con-
taining electron-donor or electron-acceptor substituents (Table 2). As
illustrated, all kinds of aldehydes delivered corresponding products in
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Applied Surface Science Advances 5 (2021) 100096
high yield (Table 2). These findings confirm high ability of the present
catalyst for production of different 2-amino-3-cyanopyridines.
Due to the recoverability and reusability are important character-
istic of heterogeneous catalytic systems in chemical processes, in the
next study these aspects of Fe3 O4 @MCM-41/Melamine nanocatalyst
were investigated. To do this, the condensation between benzaldehyde,
ammonium acetate, acetophenone and malononitrle was chosen as a
model reaction. After finishing of the reaction, the catalyst was sepa-
rated, washed with EtOH and dried. Then, the recovered Fe3 O4 @MCM-
41/Melamine was reused in the next run. These steps were repeated
and it was seen that the catalyst can be recycled for 14 runs with no
noticeable decrease in its performance (Fig. 6). The FT-IR analysis of
the recovered catalyst was next performed to study its chemical and
structural stability under the applied conditions. As shown in Fig. 7, the
FT-IR spectrum of the recovered Fe3 O4 @MCM-41/Melamine catalyst
is approximately the same as the FT-IR spectrum of the fresh catalyst,
confirming the high chemical stability of the designed material under
reaction conditions.
In the next study, the results obtained from this study were compared
with the results of former catalytic systems (Table 3). This showed that
the Fe3 O4 @MCM-41/Melamine is better than the most of other cata-
lysts in terms of reaction time, temperature and recycling runs. These
findings confirm higher applicability, durability and recoverability of
the designed catalyst than the former catalytic systems. The aforemen-
tioned advantages are attributed to stable magnetic core, well-ordered
mesoporous shell and chemically immobilized catalytic sites of the de-
signed material.
Finally, a suitable mechanism was proposed to show the role
of melamine as an effective catalyst in the synthesis of 2-amino-3-
cyanopyridines (Scheme 2). As shown, in the first step, the aldehyde and
the melamine-activated malononitrile are condensed through a Knoeve-
nagel reaction to give intermediate 1. On the other hand, imine 2 is pro-
duced through treatment of the ammonium acetate with acetophenone.
Subsequently, the intermediate 1 reacts with imine 2 and the processes
Z. Haydari, D. Elhamifar, M. Shaker et al. Applied Surface Science Advances 5 (2021) 100096

Table 2
Preparation of 2-amino-3-cyanopyridine derivatives using Fe3 O4 @MCM-41/melamine.

Entry X Time (min) Yield (%)a M.P. ( °C) Found M.P. ( °C) Reported

1 H 20 95 187–189 186–187 [43]

2 3-NO2 15 92 198–200 200–202 [4]
3 4-NO2 15 94 214–216 212–213 [43]
4 4-CN 18 90 183–185 184–186 [4]
5 4-Br 20 93 224–226 225–228 [44]
6 4-Me 25 89 228–230 231–233 [4]
7 4-MeO 27 85 182–184 181–182 [43]
a
Isolated yield.

Fig. 6. Recoverability of the Fe3 O4 @MCM-

41/Melamine.

Fig. 7. FT-IR spectrum of the recovered

Fe3 O4 @MCM-41/Melamine catalyst.

6
Z. Haydari, D. Elhamifar, M. Shaker et al. Applied Surface Science Advances 5 (2021) 100096

Table 3
Comparative study between Fe3 O4 @MCM-41/Melamine and former catalytic systems.

Entry Catalyst Conditions Recovery times Ref.

1 [Fe3 O4 @SiO2 @(CH2 )3 Im]C(CN)3 Solvent free, 100 °C, 40 min 9 [4]
2 FePO4 EtOH, reflux, 4 h 4 [45]
3 Fe3 O4 @TiO2 @O2 PO2 (CH2 )NHSO3 H Solvent free, 90 °C, 20 min 7 [5]
4 GO H2 O, 80 °C, 300 min 6 [6]
5 SBPTETSA Solvent free, 100 °C, 10 min 6 [46]
6 NMS Solvent free, 80 °C, 20 min 3 [47]
7 Fe3 O4 @MCM-41/Melamine H2 O, 50 °C, ))), 20 min 14 This work

Abbreviations: [GO]: Graphene oxide, [SBPTETSA]: Silica-bound N-propyl triethylenetetramin sulfamic

acid, [NMS]: Nicotinum methane sulfonate.

Scheme 2. Proposed mechanism for the synthesis of 2-amino-3-cyanopyridines using the Fe3 O4 @MCM-41/Melamine catalyst.

of cycloaddition, isomerization, and aromatization lead to the formation 3-cyanopyridines under ultrasonic conditions. The other advantages of
of 2-amino-3-cyanopyridine 3 [48]. this work were the use of water solvent, high recoverability and reusabil-
ity of the designed catalyst, high stability of catalyst and easy separation
of products. The applications of this catalyst in other organic processes
4. Conclusion such as coupling reactions are underway in our laboratory.

In this study, synthesis, characterization and catalytic applica-

tion of a novel magnetic mesoporous silica supported melamine with
core-shell structure were developed. The characterization techniques
showed spherical particles with well coating/immobilization of nanosil-
ica shell and melamine moieties on magnetic cores. The Fe3 O4 @MCM-
41/Melamine was powerfully used in the green production of 2-amino-
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.

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Z. Haydari, D. Elhamifar, M. Shaker et al. Applied Surface Science Advances 5 (2021) 100096

Acknowledgments [25] J. Kim, J.E. Lee, J. Lee, J.H. Yu, B.C. Kim, K. An, Y. Hwang, C.H. Shin, J.G. Park,
J. Kim, Magnetic fluorescent delivery vehicle using uniform mesoporous silica
spheres embedded with monodisperse magnetic and semiconductor nanocrystals,
The authors acknowledge the Yasouj University and the Iran J. Am. Chem. Soc. 128 (2006) 688–689.
National Science Foundation (INSF) for supporting this work. [26] W. Zhao, J. Gu, L. Zhang, H. Chen, J. Shi, Fabrication of uniform magnetic nanocom-
posite spheres with a magnetic core/mesoporous silica shell structure, J. Am. Chem.
References Soc. 127 (2005) 8916–8917.
[27] R. Pourhasan-Kisomi, F. Shirini, M. Golshekan, Introduction of organic/inorganic
Fe3 O4 @ MCM-41@ Zr-piperazine magnetite nanocatalyst for the promotion of the
[1] J. Tang, L. Wang, Y. Yao, L. Zhang, W. Wang, One-pot synthesis of
synthesis of tetrahydro-4H-chromene and pyrano [2, 3-d] pyrimidinone derivatives,
2-amino-3-cyanopyridine derivatives catalyzed by ytterbium perfluorooctanoate [Yb
Appl. Organomet. Chem. 32 (2018) e4371.
(PFO)3 ], Tetrahedron lett. 52 (2011) 509–511.
[28] J. Mondal, T. Sen, A. Bhaumik, Fe3 O4 @ mesoporous SBA-15: a robust and mag-
[2] N.M. Evdokimov, A.S. Kireev, A.A. Yakovenko, M.Y. Antipin, I.V. Magedov, A. Ko-
netically recoverable catalyst for one-pot synthesis of 3, 4-dihydropyrimidin-2 (1
rnienko, One-step synthesis of heterocyclic privileged medicinal scaffolds by a mul-
H)-ones via the Biginelli reaction, Dalton Trans. 41 (2012) 6173–6181.
ticomponent reaction of malononitrile with aldehydes and thiols, J. Org. Chem. 72
[29] Y. Snoussi, S. Bastide, M. Abderrabba, M.M. Chehimi, Sonochemical synthesis of
(2007) 3443–3453.
Fe3 O4 @ NH2 -mesoporous silica@ polypyrrole/Pd: a core/double shell nanocompos-
[3] D. Bora, B. Deb, A.L. Fuller, A.M. Slawin, J.D. Woollins, D.K. Dutta, Dicarbonylirid-
ite for catalytic applications, Ultrason. Sonochem. 41 (2018) 551–561.
ium (I) complexes of pyridine ester ligands and their reactivity towards various elec-
[30] S. Luo, G. Fan, M. Luo, J. Li, G. Song, Synthesis of styrene carbonate from styrene
trophiles, Inorg. Chim. Acta 363 (2010) 1539–1546.
oxide and CO2 over ZnBr2 supported on MCM-41—Coated magnetic Fe3 O4 , J. CO2
[4] M.A. Zolfigol, M. Kiafar, M. Yarie, A.A. Taherpour, M. Saeidi-Rad, Experimental
Util. 14 (2016) 23–30.
and theoretical Studies of the nanostructured {Fe3 O4 @ SiO2 @(CH2 )3 Im} C (CN)3
[31] S.S.A.D.M. Abadi, M. Abdollahi-Alibeik, Fe3 O4 @ FeSO4 -MCM-41 nanoparticles and
catalyst for 2-amino-3-cyanopyridine preparation via an anomeric based oxidation,
reusable catalyst for the synthesis of quinoxalines in solvent-free conditions, Silicon
RSC Adv. 6 (2016) 50100–50111.
10 (2018) 1667–1678.
[5] M.A. Zolfigol, M. Yarie, Fe3 O4 @ TiO2 @ O2 PO2 (CH2 ) NHSO3 H as a novel nanomag-
[32] W. Xie, Y. Han, H. Wang, Magnetic Fe3 O4 /MCM-41 composite-supported sodium sil-
netic catalyst: application to the preparation of 2-amino-4, 6-diphenylnicotinoni-
icate as heterogeneous catalysts for biodiesel production, Renew. Energy 125 (2018)
triles via anomeric-based oxidation, Appl. Organomet. Chem. 31 (2017) e3598.
675–681.
[6] D. Khalili, Graphene oxide: a reusable and metal-free carbocatalyst for the one-pot
[33] Z. Ramazani, D. Elhamifar, M. Norouzi, R. Mirbagheri, Magnetic mesoporous
synthesis of 2-amino-3-cyanopyridines in water, Tetrahedron lett. 57 (2016)
MCM-41 supported boric acid: a novel, efficient and ecofriendly nanocomposite,
1721–1723.
Compos. B Eng. 164 (2019) 10–17.
[7] F. Tamaddon, D. Azadi, Synthesis and identification of nicotinium sulfate
[34] M. Norouzi, D. Elhamifar, Ionic liquid-modified magnetic mesoporous silica sup-
(3-(1-methylpyrrolidin-2-yl) pyridine: H2SO4) from tobacco-extracted nicotine: a
ported tungstate: a powerful and magnetically recoverable nanocatalyst, Compos. B
protic ionic liquid and biocompatible catalyst for selective acetylation of amines, J.
Eng. 176 (2019) 107308.
Mol. Liq. 255 (2018) 406–412.
[35] M. Shaker, D. Elhamifar, Magnetic Ti-containing phenylene-based mesoporous
[8] Y.H. Kim, S.J. Park, Roles of nanosized Fe3 O4 on supercapacitive properties of car-
organosilica: a powerful nanocatalyst with high recoverability, Colloids Surf. A
bon nanotubes, Curr. Appl. Phys. 11 (2011) 462–466.
Physicochem. Eng. Asp. 608 (2020) 125603.
[9] L. Cabrera, S. Gutierrez, N. Menendez, M. Morales, P. Herrasti, Magnetite nanopar-
[36] M. Norouzi, D. Elhamifar, R. Mirbagheri, Phenylene-based periodic mesoporous
ticles: electrochemical synthesis and characterization, Electrochim. Acta 53 (2008)
organosilica supported melamine: an efficient, durable and reusable organocatalyst,
3436–3441.
Microporous Mesoporous Mater. 278 (2019) 251–256.
[10] A.H. Lu, E.E.L. Salabas, F. Schüth, Magnetic nanoparticles: synthesis, protection,
[37] F. Adam, K.M. Hello, H. Osman, The heterogenation of melamine and its catalytic
functionalization, and application, Angew. Chem. Int. Ed. 46 (2007) 1222–1244.
activity, Appl. Catal. A 382 (2010) 115–121.
[11] C.Y. Haw, F. Mohamed, C. Chia, S. Radiman, S. Zakaria, N. Huang, H. Lim, Hy-
[38] J.N. Appaturi, R.J. Ramalingam, H.A. Al-Lohedan, Synthesis, characterization and
drothermal synthesis of magnetite nanoparticles as MRI contrast agents, Ceram. Int.
catalytic activity of melamine immobilized MCM-41 for condensation reactions, J.
36 (2010) 1417–1422.
Porous Mater. 25 (2018) 629–641.
[12] M.B. Gawande, Y. Monga, R. Zboril, R. Sharma, Silica-decorated magnetic nanocom-
[39] M. Neysi, A. Zarnegaryan, D. Elhamifar, Core–shell structured magnetic silica sup-
posites for catalytic applications, Coord. Chem. Rev. 288 (2015) 118–143.
ported propylamine/molybdate complexes: an efficient and magnetically recover-
[13] N.A. Frey, S. Peng, K. Cheng, S. Sun, Magnetic nanoparticles: synthesis, function-
able nanocatalyst, New J. Chem. 43 (2019) 12283–12291.
alization, and applications in bioimaging and magnetic energy storage, Chem. Soc.
[40] R. Mirbagheri, D. Elhamifar, Magnetic ethyl-based organosilica supported Schif-
Rev. 38 (2009) 2532–2542.
f-base/indium: a very efficient and highly durable nanocatalyst, J. Alloy. Compd.
[14] J. Liu, S.Z. Qiao, Q.H. Hu, G.Q. Lu, Magnetic nanocomposites with mesoporous struc-
790 (2019) 783–791.
tures: synthesis and applications, Small 7 (2011) 425–443.
[41] M. Shaker, D. Elhamifar, Sulfonic acid supported on magnetic methylene-based
[15] N.Z. Knezevic, C.M. Jimenez, M. Albino, A. Vukadinovic, A. Mrakovic, E. Illes,
organosilica as an efficient and recyclable nanocatalyst for biodiesel production via
D. Janackovic, J.O. Durand, C. Sangregorio, D. Peddis, Synthesis and characteriza-
esterification, Front. Energy Res. 8 (2020) 78.
tion of core-shell magnetic mesoporous silica and organosilica nanostructures, MRS
[42] Z.C. Wu, Z.Z. Wang, J. Liu, J.H. Yin, S.P. Kuang, A new porous magnetic chitosan
Adv. 2 (2017) 1037–1045.
modified by melamine for fast and efficient adsorption of Cu(II) ions, Int. J. Biol.
[16] C.L. Li, B.R. Huang, J.Y. Chang, J.K. Chen, Bifunctional superparamagnetic–lumi-
Macromol. 81 (2015) 838–846.
nescent core–shell–satellite structured microspheres: preparation, characterization,
[43] M.M. Heravi, S.Y.S. Beheshtiha, M. Dehghani, N. Hosseintash, Using magnetic
and magnetodisplay application, J. Mater. Chem. C 3 (2015) 4603–4615.
nanoparticles Fe3 O4 as a reusable catalyst for the synthesis of pyran and pyridine
[17] H. Mahmoudi, A.A. Jafari, S. Saeedi, H. Firouzabadi, Sulfonic acid-functionalized
derivatives via one-pot multicomponent reaction, J. Iran. Chem. Soc. 12 (2015)
magnetic nanoparticles as a recyclable and eco-friendly catalyst for atom economical
2075–2081.
Michael addition reactions and bis indolyl methane synthesis, RSC Adv. 5 (2015)
[44] J. Safari, S.H. Banitaba, S.D. Khalili, Ultrasound-promoted an efficient method for
3023–3030.
one-pot synthesis of 2-amino-4, 6-diphenylnicotinonitriles in water: a rapid proce-
[18] A. Schätz, O. Reiser, W.J. Stark, Nanoparticles as semi-heterogeneous catalyst sup-
dure without catalyst, Ultrason. Sonochem. 19 (2012) 1061–1069.
ports, Chem. Eur. J. 16 (2010) 8950–8967.
[45] M. Zadpour, F.K. Behbahani, Iron (III) phosphate as a green and reusable catalyst for
[19] Z. Xu, Y. Hou, S. Sun, Magnetic core/shell Fe3 O4 /Au and Fe3 O4 /Au/Ag nanoparti-
the synthesis of 4, 6-disubstituted 2-aminopyridine-3-carbonitriles, Monatsh. Chem.
cles with tunable plasmonic properties, J. Am. Chem. Soc. 129 (2007) 8698–8699.
146 (2015) 1865–1869.
[20] D. Tang, R. Yuan, Y. Chai, Magnetic core− shell Fe3 O4 @ Ag nanoparticles coated
[46] K. Niknam, A. Jamali, M. Tajaddod, A. Deris, Synthesis of 2-amino-4, 6-diarylni-
carbon paste interface for studies of carcinoembryonic antigen in clinical immunoas-
cotinonitriles using silica-bound N-propyl triethylenetetramine sulfamic acid as a
say, J. Phys. Chem. B 110 (2006) 11640–11646.
recyclable solid acid catalyst, Chin. J. Catal. 33 (2012) 1312–1317.
[21] C.R. Vestal, Z.J. Zhang, Atom transfer radical polymerization synthesis and magnetic
[47] F. Tamaddon, D. Azadi, Nicotinium methane sulfonate (NMS): a bio-renewable pro-
characterization of MnFe2 O4 /polystyrene core/shell nanoparticles, J. Am. Chem.
tic ionic liquid and bi-functional catalyst for synthesis of 2-amino-3-cyano pyridines,
Soc. 124 (2002) 14312–14313.
J. Mol. Liq. 249 (2018) 789–794.
[22] Y. Deng, D. Qi, C. Deng, X. Zhang, D. Zhao, Superparamagnetic high-magnetization
[48] M. Afradi, S.A. Pour, M. Dolat, A. Yazdani-Elah-Abadi, Nanomagnetically modified
microspheres with an Fe3 O4 @ SiO2 core and perpendicularly aligned mesoporous
vitamin B3 (Fe3O4@ Niacin): an efficient and reusable green biocatalyst for mi-
SiO2 shell for removal of microcystins, J. Am. Chem. Soc. 130 (2008) 28–29.
crowave-assisted rapid synthesis of 2-amino-3-cyanopyridines in aqueous medium,
[23] L.M. Rossi, N.J. Costa, F.P. Silva, R. Wojcieszak, Magnetic nanomaterials in catalysis:
Appl. Organomet. Chem. 32 (2018) e4103.
advanced catalysts for magnetic separation and beyond, Green Chem. 16 (2014)
2906–2933.
[24] P. Riente, C. Mendoza, M.A. Pericás, Functionalization of Fe3 O4 magnetic nanopar-
ticles for organocatalytic Michael reactions, J. Mater. Chem. 21 (2011) 7350–7355.