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OPEN Functionalization of magnetic

nanoparticles by creatine as a novel
and efficient catalyst for the green
synthesis of 2‑amino‑4H‑chromene
derivatives
Reza Eivazzadeh‑Keihan, Shahrzad Bahrami, Mostafa Ghafori Gorab, Zahra Sadat &
Ali Maleki*

By employing the naturally-originated molecule of creatine, ­Fe3O4@SiO2-creatine as an

environmentally benign magnetic organometallic nanobiocatalyst was successfully prepared via
a convenient and green route. Then to acquire an inclusive comprehension of different properties
of the catalyst, it was studied by various characterization techniques such as FT‐IR, FE-SEM, TEM,
EDX, XRD, and VSM analyses. It was found that the size distribution of nanoparticles was an average
diameter size of 70 nm. To examine the catalytic activity, it was applied in sequential knoevenagel
condensation-Michael addition room temperature reaction of dimedone, malononitrile, and
different substituted aromatic aldehydes to produce a variety of 2-amino-tetrahydro-4H-chromene-
3-carbonitrile derivatives in a single step. Among the multiple outstanding advantages that can be
mentioned for this work, some of the most noticeable ones include: affording the products in short
reaction times with high yields, operating the reaction at ambient conditions and ease of catalyst
separation.

In the last decades, due to growing concerns about environmental contamination and its extensive detrimental
effect on earth’s ecosystems, designing more environmentally benign chemical processes has attracted substantial
attention. Global interest has recently shifted into developing more eco-friendly synthetic approaches to accom-
plish the most important goal of green chemistry which is stopping or decreasing the use and generation of haz-
ardous and toxic ­chemicals1–3. In this regard, great efforts have been made to the use of bio-based feed stocks such
as ­cellulose4,5, ­chitosan6,7, alginic ­acid8,9 and newly, creatine as natural supports in designing and producing differ-
ent ­catalysts10. Creatine is a naturally occurring nitrogen-containing organic acid that exists primarily in muscle
tissue of vertebrates and plays a very significant role in the energy supply process for muscle tissue by participat-
ing in recycling adenosine triphosphate (ATP) via giving a phosphate group to adenosine diphosphate (ADP)10.
Creatine’s natural production in the human body mainly takes place in the liver and kidneys and includes the
enzyme-promoted reaction between glycine and arginine amino acids to form g­ uanidinoacetate11. Then, in the
second step, enzyme-assisted methylation of guanidinoacetate using s-adenosyl methionine as the methyl-group
donor produce creatine. After that, the as-synthesized creatine is being transferred to the muscles through the
bloodstream. Apart from the major bio-synthesized supply of creatine, it can also be obtained from the ­diet12.
Since creatine is naturally originated, it doesn’t have any harmful effect on living systems and affords the demand
of chemists to employ green and natural materials. Having both carboxylic and amine groups, creatine is capable
of activating raw materials both in acid-catalyzed reactions as well as base-catalyzed reactions; so, it has attracted
chemist’s attention as a potential bifunctional catalyst. Herein, by supporting this biocompatible, non-toxic and
biodegradable molecule on a magnetic core, a novel reusable organometallic superparamagnetic creatine-based
nanobiocatalyst was designed, prepared, characterized and then it was employed in a one-pot three-component
condensation reaction for the synthesis of 2-amino-tetrahydro-4H-chromene-3-carbonitrile. In addition to
have a broad spectrum of biological and pharmacological properties such as ­antitumor13,14, ­antibacterial15–17,
­antiviral18, ­antifungal19, anti-influenza20, anti-inflammatory21, ­anticancer22,23, and antiallergenic a­ ctivity24,25, these

Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and
Technology, Tehran 16846‑13114, Iran. *email: maleki@iust.ac.ir

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oxygen-containing heterocyclic scaffolds exhibits a lot of industrial applications in the field of cosmetics and
­pigments26, laser ­dyes27, photoactive m
­ aterials28, optical brighteners, fluorescent m
­ arkers29 and biodegradable
30,31
­agrochemicals . Due to their wide range of applications, there exist several reports of employing homogene-
ous and heterogeneous catalysts to promote the synthesis of 2-amino-tetrahydro-4H-chromene-3-carbonitrile
­frameworks32–42. Although all of these catalysts offer some advantages, many of them suffer from different defects
such as the requirement of energy inputs like microwaves or ultrasonic irradiation or high temperature, using of
toxic and expensive solvents, catalysts and reagents, long reaction times, high catalyst loading, tedious workup
procedures, and low yields. Our green efficient protocol for production of 2-amino-tetrahydro-4H-chromene-
3-carbonitriles consist of three-component catalytic reaction between malononitrile, an aldehyde, and dimedone
and is catalyzed by above-mentioned nanobiocatalyst. Through bio-functionalizing the surface of magnetic
nanoparticles (MNPs) with creatine, the core–shell ­Fe3O4@SiO2-creatine nanocatalyst was successfully prepared.
Recently a large number of researches have been focused on magnetic nanoparticles because of their remarkable
features like providing high surface, facilitating catalyst separation and product purification and lot of other
­merits43,44. Due to the magnetic characteristic of this creatine-functionalized catalyst, it can be easily collected
from the reaction mixture by a magnet bar which eliminates the possibility of the presence of remained catalyst
particles in the pharmaceutical final products.

Experimental
General. All solvents, chemicals, and reagents were purchased from Merck, Sigma and Aldrich. Thin-layer
chromatography (TLC) was used to monitor the progress of catalytic reactions. Melting points were measured
with an Electrothermal 9100 apparatus. FT‐IR spectra were recorded on a Shimadzu IR‐470 spectrometer using
KBr pellets. Elemental analysis of the nanocatalyst was carried out by EDX analysis recorded on Numerix JEOL-
JDX 8030 (30 kV, 20 mA). XRD pattern of nanocomposite was recorded on an X′ Pert Pro X-ray diffractometer
operating at 40 mA current and 40 kV. 1H and 13C NMR spectra were recorded on a Bruker DRX‐500 Avance
spectrometer at 500 and 125 MHz, respectively. The morphology and structure of the nanocatalyst were exam-
ined by FE-SEM, MIRA3 TESCAN. TEM measurements were carried out on a Zeiss-EM10C-100 kV analyzer
to prove the core–shell structure of the nanocomposite. The magnetic properties of the samples were detected at
room temperature using a VSM of Meghnatis Daghigh Kavir.

Synthesis of the nanobiocatalyst. The preparation of the nanobiocatalyst was carried out using simple
and readily available precursors via four steps including the synthesis of F­ e3O4 core, coating the magnetic core
by silica shells, immobilizing creatine as an external shell, respectively.

Synthesis of F
­ e3O4 NPs. Fe3O4 NPs were synthesized via co-precipitation ­method45. Typically, 4.70 g F
­ eCl3·6H2O
and 1.72 g ­FeCl2·4H2O (with a molar ratio of 2:1) were mixed with 80 mL of distilled ­H2O in a round bot-
tom flask under ­N2 atmosphere. The temperature was gradually increased up to 80 °C and at this point, 10 mL
­NH3·H2O (25% v/v) was added dropwise to the vigorously stirring above-mentioned mixture. After the addition
of ammonia, stirring of the mixture was continued for 45 min and then it was cooled to room temperature. The
resulting black sediment was aggregate with an external magnet and was frequently washed with distilled water,
ethanol and acetone in turn and dried at 70 °C in an oven in order to make it ready for further modifications.

Synthesis of F
­ e3O4@SiO2 NPs. Coating the magnetic ­Fe3O4 core with a layer of ­SiO2 was performed through
a modified Stöber ­method46. Initially, 2.00 g of as-prepared ­Fe3O4 NPs were dispersed in a mixture of 160 mL
ethanol and 40 mL distilled water for 15 min using an ultrasonic water bath. Later, 10 mL of ammonia solution
(25 wt%) was injected dropwise to the reaction mixture under intensive magnetic stirring. In the next step, 1 mL
of TEOS was dropped slowly into the solution by a syringe for 20 min. in the last step, the mixture allowed to stir
for 12 h at room temperature. Finally, the brown obtained solid was collected by a magnet and after successive
washing with distilled water and ethanol several times it was dried at 60 °C.

Preparation of chloropropyl‑functionalized ­ Fe3O4@SiO2 MNPs. Binding (3-chloropropyl)-trimethoxysilan

(CPTMS) as a linker to silica-coated MNPs was performed following the procedure of one of previous w ­ orks47.
Firstly, 1 mL of CPTMS reagent was dissolved in 100 mL of dried toluene. afterward, 1.00 g of ­Fe3O4@SiO2 was
added to this mixture and the solution stirring last for 18 h at 60 °C. The resulted brown precipitate ­(Fe3O4@
SiO2‒Cl) was washed with toluene, separated by a permanent magnet, and vacuum dried at 70 °C.

Synthesis of ­Fe3O4@SiO2‑creatine. At first, 1.00 g of as-prepared F ­ e3O4@SiO2–Cl nanoparticle and 1.31 g

(10 mmol) of creatine were added to 80 mL of ethanol and the mixture was stirred in a round bottom flask under
refluxing conditions for 10 h. Then, the obtained solid substance was magnetically separated, washed repetitively
with distilled water, ethanol and acetone and dried at 70 °C in an oven.

General procedure for the synthesis of 4H‑chromene derivatives (4a–o). First, 1.00 mmol (0.14 g) dimedone,
1.00 mmol of aromatic aldehydes and 1.10 mmol (0.07 g) malononitrile were mixed together in 2 mL of ethanol
in presence of 0.04 g of the prepared catalyst. This mixture stirred for appropriate times at room temperature.
The progress of the reaction was monitored by TLC (ethyl acetate: n-hexane, 1:1). After completion of the reac-
tion, the catalyst was separated using an external magnet and the obtained precipitates which were the products,
recrystallized in ethanol to gain highly pure crystalline 4H-chromene compounds.

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Figure 1.  Preparation of creatine-functionalized F

­ e3O4@SiO2 NPs and synthesis of 4H-chromene derivatives
(4a–o).

Results and discussion

In this study, a unique bifunctional nanobiocatalyst with acidic and basic sites was designed by immobilizing
creatine on the surface of ­Fe3O4@SiO2 NPs. At first, ­Fe3O4@SiO2 NPs were synthesized. In the second step, these
NPs were modified by biomolecule of creatine as an environmentally friendly and low-cost compound (Fig. 1).
Several identification techniques such as FT-IR, EDX, FE-SEM, TEM, and VSM were employed to study the
properties of the nanocatalyst. Also, after several times using it as a bifunctional catalyst for the synthesizing of
2‐amino‐4H‐chromenes, there was no specific changing in the structure and activity of the mentioned catalyst.

Characterization of the nanocatalyst. FT‑IR spectroscopy. FT-IR spectra of ­Fe3O4@SiO2–Cl and the
final creatine-coated MNPs are depicted in Fig. 2a,b. As can be seen in the spectrum Fig. 2a, the peak appeared
at 576 ­cm−1 is ascribed to F ­ e2+–O–Fe2+ and the one at 632 ­cm−1 to F
­ e3+–O–Fe3+ stretching ­vibrations48,49. The
sharp band appearing at 1089 ­cm−1 is attributed to asymmetric stretching vibration and the one at 802 ­cm−1
symmetric stretching vibrations of Si–O–Si ­bond50. The absorption peaks of the ­Fe3O4@SiO2–Cl at 2894 ­cm−1
and 2964 ­cm−1 are related to the symmetric and asymmetric stretching vibration of C–H ­bonds44. Additionally,
peaks appeared at about 3300 ­cm−1 are assigned to the asymmetric stretching vibration of hydroxyl groups on the
surface of the silica layer. Coating of magnetic core with the organo-layer of creatine is confirmed by stretching
vibrations appeared at 1683 ­cm−1 which is related to C=O functional group of creatine biomolecule (Fig. 2b)51.
Peaks appeared in the IR spectrum of the composite are very good in agreement with functional groups existing
in the structure of the organo-functionalized MNPs and could be counted as evidence to approve the core–shell
structure of as-described nanocatalyst.

EDX analysis. EDX analysis was performed to determine the elements in the composition of the catalyst. The
result of EDX analysis is demonstrated in Fig. 2c. It clearly indicated the existence of iron, silicon, carbon, oxygen
and nitrogen elements in the nanobiocomposite. The presence of the Fe peaks in the EDX result indicates the
existence of ­Fe3O4 nanoparticles in the structure. In addition, silicon and nitrogen peaks are clear signs of TEOS
and creatine, respectively. Carbon and oxygen peaks are related to the presence of these elements in TEOS and
creatine molecules. The observed oxygen peak is also related to F ­ e3O4 nanoparticles.

FE‑SEM image study. In order to identify the surface morphology and particle size distribution of the nano-
catalyst FE-SEM imaging technique was used (Fig. 3a–d). As can be observed in SEM micrographs in four dif-
ferent magnifications, the ­Fe3O4@SiO2-creatine nanoparticles have an approximately spherical shape and size
distribution with an average diameter length of 70 nm.

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Figure 2.  FT-IR spectra of (a) chloropropylated F

­ e3O4@SiO2 MNP, (b) ­Fe3O4@SiO2-creatine nanobiocomposite
and (c) EDX analysis of F
­ e3O4@SiO2-creatine nanobiocomposite.

TEM image study. To determine the structure of interior layers of the synthesized nanobiocatalyst and to prove
the core–shell structure of it, TEM analysis was utilized. As it is observable in Fig. 4. TEM images were taken in
3 different magnifications 150 nm (Fig. 4a), 60 nm (Fig. 4b), 30 nm (Fig. 4c) which clearly show the shell consist-
ing of silica inorganic layers and organic layer of creatine that have coated F
­ e3O4 core.

VSM analysis. Magnetic characteristic of the ­Fe3O4@SiO2-creatine nanocatalyst was measured via VSM analy-
sis at room temperature (300 K). Figure 5 shows the magnetization as a function of magnetic field strength. The
saturation magnetization value (Ms) of uncoated MNPs (­ Fe3O4) (Fig. 5a) was found to be 56.0 emu g­ −152. With
sweeping the magnetic field from − 20,000 to + 20,000 oersted, the saturation magnetization value (Ms) of the
prepared nanocomposite was found to be about 22.5 emu ­g−1 (Fig. 5b), which is lower than neat ­Fe3O4 NPs. This
reduction in the saturation magnetization is mostly ascribed to the existence of shells that have wrapped the
­Fe3O4 core. Despite this reduction in the saturation magnetization of catalyst, the intensity of its magnetic power
is still high and can be easily separated from the reaction media by an external magnet. Moreover, the resultant
hysteresis loop clearly certifies the superparamagnetic characteristic of the prepared nanocomposite.

X‑ray diffraction (XRD). The XRD pattern of the synthesized nanocatalyst in comparison with that of pure
­Fe3O4 is studied in a range of 5–80° and the resulting diffraction pattern is depicted in Fig. 6.
Characteristic diffraction peaks of the catalyst observed at 2θ = 18.38°, 30.32°, 35.70°, 43.33°, 53.82°, 57.38°,
62.95°, 74.31° respectively correspond to (1 1 1), (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), (4 4 0), (5 3 3) crystal

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Figure 3.  SEM images of ­Fe3O4@SiO2-creatine nanobiocatalyst in four different magnifications: (a) 500 nm, (b)
200 nm and (c) 100 nm and (d) 1 μm.

planes of pure ­Fe3O4 with cubic inverse spinel structure. The location and relative intensities of all diffraction
peaks are in good agreement with the standard XRD pattern of magnetite (JCPDS card No.01-075-0449), repre-
senting that cubic crystalline spinel structure of F
­ e3O4 have not changed during functionalization with creatine.
Moreover, the broad peak from 2θ = 20° to 27° is referred to amorphous silica phase in the catalyst shell which
can be declared as another proof that shows silica layers have successfully coated ­Fe3O4 NPs.

Application of the nanobiocatalyst in organic synthesis. In order to investigate the catalytic activ-
ity of the created nanocatalyst, it was utilized in the one-pot synthesis of 2-amino-7,7-dimethyl-5-oxo-4-aryl-
hexahydro-4H-chromene-3-carbonitrile derivatives. To optimize the reaction condition, the reaction between
dimedone 3, 4-isopropylbezaldehyde 2, and malononitrile 1 (with a mole ratio of 1:1:1.1) in 2 mL of ethanol as
a green solvent and at room temperature, was chosen as the model reaction.

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Figure 4.  TEM images of ­Fe3O4@SiO2-creatine nanobiocatalyst in three different magnifications: (a) 150 nm,
(b) 60 nm and (c) 30 nm.

Figure 5.  VSM magnetization curve of: (a) ­Fe3O4 and (b) ­Fe3O4@SiO2-creatine.

At first, the effect of catalyst amount on the reaction rate and yield was studied. Using 0.04 g of the nano-
catalyst was found to be adequate to catalyze the reaction and produce high yields of 4H-chromene derivatives.
According to Table 1, in the presence of lower amounts of catalysts, lower yields of the products were obtained
and the reaction took a longer time to complete. With increasing the amount of nanocatalyst no significant
improvement in the reaction rate and yield was observed. As shown in Table 1, only trace amounts of the desired
products were obtained in the absence of the nanocatalyst. To optimize the solvent of the reaction, the effect of
­H2O as another green solvent has also been studied. Finally, based on the results, ethanol was found to be the
most suitable solvent (Table 1, entry 7). Since the desired products were produced in high to excellent yield at
room temperature, testing higher temperatures were not needed.
In order to compare the efficiency of the prepared catalyst with its substrate before coating with creatine, the
model reaction was performed with 0.04 g of each of the catalysts mentioned in Table 2. As can be seen in the
table, at a specified time the efficiency of the prepared catalyst is much more than the substrates alone. F ­ e 3O 4
allows the catalyst to be easily separated from the reaction medium by an external magnet. In addition, F ­ e 3O 4
as Lewis acid can increase the reaction rate. Creatine as a proton donor agent activates electrophiles and also

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Figure 6.  XRD pattern of ­Fe3O4@SiO2-creatine nanobiocatalyst.

Entry Catalyst loading (g) Solvent Temp (°C) Time (min) Yielda (%)
1 – – r.t 60 Trace
2 – – 80 60 25
3 – EtOH r.t 60 20
4 0.01 EtOH r.t 45 45
5 0.02 EtOH r.t 30 60
6 0.03 EtOH r.t 20 80
7 0.04 EtOH r.t 12 91
8 0.05 EtOH r.t 12 91
9 0.04 H2O r.t 15 85
10 0.04 – r.t 30 70

Table 1.  Optimizing the reaction conditions in the synthesis of 2‐amino‐4H‐chromene derivatives. a The yields
refer to the isolated product 4h.

Entry Catalyst Yielda (%)

1 Fe3O4 40
2 Fe3O4@SiO2 45
3 Creatine 60
4 Fe3O4@SiO2-creatine 91

Table 2.  Comparison of catalytic activity of the prepared catalyst with the substrates alone. a Isolated yield.

modifies nucleophilic reactions in the mechanism. The nitrogen in the structure of nanobiocatalyst acts as a base
and improves the nucleophilic reaction of malononitrile and aldehyde by separating the acidic hydrogen from
malononitrile. The synthesized nanobiocatalyst improves the reaction conditions by having a large number of
acid–base parts.
In order to show the repeatability of this approach and to generalize the optimum conditions to other aromatic
aldehyde a wide range of substituted benzaldehydes bearing both electron-withdrawing and electron-donating
groups were chosen and the reactions of those aldehydes (2) with malononitrile (1) and dimedone (3) has led
to the formation of a diverse sort of 2‐amino‐4H‐chromene-3-carbonitrile derivatives under optimum reaction
conditions. The results presented in Table 3 show all products were successfully synthesized in good‐to‐excellent
yields after suitable reaction time. Moreover, the results indicated that aldehydes possessing electron-withdrawing
groups reacted much faster and gave higher yields than those bearing electron-releasing groups, however, the
yield of the products with aldehyde bearing electron-releasing groups was completely satisfying in comparison
with previous ­works53–55.
The suggested possible mechanism of the reaction in the presence of the nanocatalyst is described in Fig. 7.
Creatine as a bifunctional molecule can significantly catalyze the chromene formation reaction. Initially, the
acidic hydrogen atom of the catalyst activates the aromatic aldehyde through protonation of its carbonyl group.
So, the electrophilicity of the carbonyl group increases. Concurrently, the Nitrogen atoms in the guanidine part

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Mp (°C)
Entry Aldehyde Product Time (min) Yielda (%) Observed Literature
1 4-nitrobenzaldehyde 4a 5 96 176–182 176–18356
2 3-nitrobenzaldehyde 4b 4 96 204–207 204–20657
3 2-chlorobenzaldehyde 4c 4 96 212–215 213–21558,59
4 3-chlorobenzaldehyde 4d 7 92 228–232 229–23260
5 4-chlorobenzaldehyde 4e 6 94 214–217 214–21659
6 3-methylbenzaldehyde 4f 10 88 197–200 198–20061
7 4-methylbenzaldehyde 4g 10 86 215–219 215–21862
8 4-isopropylbenzaldehyde 4h 12 91 196–200 198–20061
9 2-methoxybenzaldehyde 4i 12 84 202–204 203–20756
10 3-methoxybenzaldehyde 4j 8 86 197–200 197–19963
11 4-methoxybenzaldehyde 4k 10 86 194–197 194–19664–66
12 3,4,5-trimethoxybenzaldehyde 4l 9 91 175–177 175–17967
13 3-hydroxybenzaldehyde 4m 15 82 233–235 232–23468
14 4-hydroxybenzaldehyde 4n 18 81 208–210 208–21069
15 2,4-dichlorobenzaldehyde 4o 6 94 118–120 118–12070

Table 3.  Synthesis of 2‐amino‐4H‐chromene derivatives using creatine-based catalyst. a Isolated yields.

Figure 7.  Proposed mechanism for the synthesis of 2‐amino‐4H‐chromene derivatives in presence of ­Fe3O4@
SiO2-creatine.

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Entry Catalyst Solvent Reaction time Yield (%) References

72
1 Melamine H2O/EtOH (3;2) 25 min 93
73
2 Aminopropylated sillica gel H2O 90 min 89
74
3 – 2,2,2-trifluoroethanol 5h 85
75
4 Nano ­SiO2 H2O 10 min 90
76
5 2-aminopyridine EtOH 8 min 92
77
6 MNPs·GO-CysA H2O/EtOH (3;1) 15 min 95
78
7 Fluoride ion H2O 30 min 84
8 Fe3O4@SiO2-creatine EtOH 4 min 96 This research

Table 4.  Comparison of the catalytic ability of ­Fe3O4@SiO2-creatine with previous reports for synthesis of 4c.

Figure 8.  Reusability of ­Fe3O4@SiO2-creatine nanobiocatalyst for the synthesis of 4c.

of the creatine (basic site of the catalyst) activates malononitrile via removing one of its acidic hydrogen a­ toms71.
Then, the occurrence of a Knoevenagel condensation through Nu attack of active malononitrile carbanion to
activated aldehyde along with excretion of a water molecule forms arylidene malononitrile intermediate (I). In
the next step, tautomerization of dimedone takes place by the acidic part of the catalyst, and intermediate (II)
is prepared. Then Michael addition of the enolized form of dimedone (II) to Knoevenagel adduct (I) is accom-
plished and intermediate (III) is prepared. Subsequently, the acidic part of the catalyst forms a hydrogen bond
with nitrogen of CN, and by increasing the electrophilic property of CN, cyclization is done. At this step, inter-
mediate (IV) is formed. Eventually, the basic site of the catalyst separates an acidic hydrogen from intermediate
(IV) and the desired product is formed.
In addition, the catalytic activity of ­Fe3O4 @ ­SiO2-creatine was evaluated in comparison with other catalysts,
and the results are shown in Table 4. As can be seen, the F ­ e3O4@SiO2-creatine catalyst performs better than
other studies.

Catalyst recyclability. The reusability of the catalyst was assessed in the synthesis of 4H-chromene deriva-
tives under optimum reaction conditions. Owing to its magnetic nature, the catalyst was easily separated from
the reaction mixture by an external magnet, washed repeatedly with ethanol and distilled water, dried and reused
after each run. It was observed that the catalyst could be reused for at least six times without any significant loss
in its activity (Fig. 8). The result of EDX analysis (Fig. S19) and FT-IR spectrum (Fig. S20) of the reused catalyst
showed no change in the composition of the catalyst.

Conclusions
In summary, a novel and green renewable creatine-functionalized magnetic nanobiocomposite catalyst was
designed and prepared via a facile, simple and cost-effective method beginning from readily accessible and non-
toxic starting materials. Subsequently, in order to investigate the catalytic activity of the prepared nanocomposite,
it was employed in the one-pot 3-CR synthesis of biologically-active 2-amino-7,7-dimethyl-5-oxo-4-aryl-hexa-
hydro-4H-chromene-3-carbonitrile derivatives. The products were obtained with the yields of 81–96% within a
few minutes. Multiple characterization techniques such as FT-IR, EDX, FE-SEM, XRD, TEM, and VSM were used
to analyze various properties of the as-synthesized organocatalyst. The FE-SEM images showed that the average
size of NPs was about 70 nm. The result of other applied identification techniques, all confirmed the formation
of the core–shell spherical structure of the nanocatalyst. The advantages of this efficient environmentally-friendly
protocol include ease of preparation and separation, providing safe and green reaction conditions, high atom
economy and excellent yields in relatively short reaction times, magnetically recyclability of the heterogeneous
catalyst, clean, simple and easy work-up procedure.

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Data availability
The datasets used and/or analysed during the current study available from the corresponding author on reason-
able request.

Received: 12 November 2021; Accepted: 13 June 2022

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Acknowledgements
The authors appreciate from the Research Council of the Iran University of Science and Technology for their
partial support of this study.

Author contributions
R.E.-K.: Substantial contributions to the conception, Design of the work, have drafted the work, Writing—Review
and Editing, Analysis and interpretation of data and wrote the main manuscript. M.G.G.: Have drafted the work,
Analysis and interpretation of data, substantively revised it. Wrote the main manuscript and prepared figures.
S.B.: Analysis and interpretation of data, substantively revised it, wrote the main manuscript and prepared fig-
ures. Z.S.: Analysis and interpretation of data, substantively revised it. A.M.: The corresponding (submitting)
author of current study, Substantial contributions to the conception, Design of the work, have drafted the work,
Writing—Review and Editing, substantively revised it.

Competing interests
The authors declare no competing interests.

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