Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646

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Environmental Nanotechnology, Monitoring & Management

journal homepage: www.elsevier.com/locate/enmm

Removal of phthalate ester compound from PVC plastic samples using

magnetic molecularly imprinted polymer on the surface of
superparamagnetic Fe3O4 (Fe3O4@MIPs)
Muhammad Ali Zulfikar a, *, Asyifa Rizqi Utami a, Nurrahmi Handayani a, *,
Deana Wahyuningrum b, Henry Setiyanto a, Muhammad Yudhistira Azis a
a
Analytical Chemistry Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia
b
Organic Chemistry Research Group, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, novel magnetic molecularly imprinted polymers (MMIPs) were successfully synthesized for se­
molecularly imprinted polymer lective separation of di(2-ethylhexyl)phthalate (DEHP) in PVC sample solutions. Polymerization was carried out
DEHP removal using Fe3O4 modified by oleic acid, ethylene glycol dimethacrylate (EGDMA), methacrylic acid (MAA), and
phthalate ester
benzoyl peroxide (BPO) in the presence of DEHP as template molecule to produce MMIPs named Fe3O4@MIPs.
Fe3O4
Magnetic non-molecularly imprinted polymers (MNIPs) were also prepared for comparison purposes. The
structure and physical properties of MMIPs and MNIPs were characterized using FT-IR, SEM, TEM, VSM and zeta
potential analysis. The FT-IR spectra showed that MMIPs were successfully synthesized, indicated by the pres­
ence of a Fe-O peak at 586 cm− 1, a benzene derivative peaks at 709, 1072, and 1155 cm− 1, a carbonyl peak of
MAA at 1728 cm− 1 and a C–H peak of oleic acid at 2954 cm− 1. SEM and TEM measurements showed that MMIPs
were porous polymers with a smaller particle size than MNIPs. VSM measurement showed that MMIPs were
superparamagnetic with a saturation magnetism value of 39.92 emu/g. MMIPs have a better adsorption capacity
than MNIPs with an imprinting factor (IF) value of 3.37 and a maximum adsorption capacity value of 17.21 mg/
g. The sorption studies showed that the adsorption process followed the Langmuir isotherm model and fitted well
to a pseudo-second-order kinetic model with ΔHo of − 82.17 kJ mol− 1. Moreover, MMIPs were more selective to
DEHP than dibutyl phthalate (DBP), with a selectivity coefficient value of 4.57. The desorption test showed that
MMIPs showed good regeneration with a desorption percentage of 98.42% and decreasing in adsorption capacity
of 11.2% after three times regenerations. DEHP removal from PVC samples using MMIP showed that polymer
could reduce the matrixes effect with a recovery percentage of around 91.03–99.68%.

1. Introduction Wezel et al., 2000).

In recent years, public health problems have been raised because of
the increasing water pollution caused by phthalate ester compounds.
Phthalates are a group of organic ester compounds commonly applied as
additives, such as plasticizers, lubricants, flooring, medical tubes,
household furniture, clothing, cosmetics, waxes, cleaning agents, and
blood bags (Giam et al., 1978; Koo and Lee, 2004). In some plastics,
phthalic esters (esters of 1, 2-benzenecarboxylic acid) are contained up
to 50 percent by weight. Their low melting point and high boiling point
properties make phthalates useful as heat and fluid transfer carrier (van
The most commonly used phthalate as a plasticizer to increase the
stability and flexibility of plastics is di(2-ethylhexyl) phthalate (DEHP)
(Lozano and Cid, 2013). DEHP in nature is a colorless, odorless, non-
volatile viscous liquid that is more soluble in non-polar substances
such as gasoline, paint remover, and oil than in water and is almost
odorless. This type of phthalate has a molecular weight (MW) of 390.56
g mol− 1 with the chemical formula C24H38O4 and consists of a pair of
eight-carbon esters linked by a benzene-dicarboxylic acid ring. The
worldwide production of DEHP reach to approximates 2 million metric
tons a year (Shelby, 2006).

* Corresponding authors.
E-mail addresses: zulfikar@chem.itb.ac.id (M. Ali Zulfikar), nurrahmi.105@itb.ac.id (N. Handayani), deana@chem.itb.ac.id (D. Wahyuningrum), henry@chem.
itb.ac.id (H. Setiyanto).

https://doi.org/10.1016/j.enmm.2022.100646
Received 29 October 2021; Received in revised form 2 January 2022; Accepted 10 January 2022
Available online 19 January 2022
2215-1532/© 2022 Elsevier B.V. All rights reserved.
M. Ali Zulfikar et al.
As a plasticizer, DEHP is used in many products, such as in the
manufacture of a wide variety of consumer products (food and bever­
ages packaging), building materials and furniture (mattresses, floor
tiles, wall coverings, and vinyl flooring), medical devices (blood bags,
nasogastric tubes, umbilical artery catheters, peritoneal dialysis bags,
and enteral nutrition feeding bags), soft plastic products (baby products
and toys), and cosmetics (Earls et al., 2003; Koniecki et al., 2011;
Rowdhwal and Chen, 2018). However, despite its benefits in improving
the quality of plastic products, DEHP can easily transfer from plastic
products to the environment because the adequate primary bonds do not
strengthen the linkage between the plastic polymer chains and the
plasticizer molecules. Consequently, humans can be exposed to these
compounds through skin absorption, ingestion and inhalation (Row­
dhwal and Chen, 2018).
Based on previously reported studies, it is known that exposure to
certain high doses of DEHP has been shown to have many adverse effects
not only in animals but also in humans. DEHP can cause very detri­
mental changes in the reproductive system, endocrine system, and
digestive system organs in rats, ferrets, mice, and hamsters (Rowdhwal
and Chen, 2018), exposure to 1500 ppm DEHP in male rats can result in
chronic progressive nephropathy (David et al., 2000), exposure to low-
doses DEHP (10 mg kg− 1) can alter brain function and behavioral
changes in some rodents (Smith et al., 2014), and was detected to cause
cancer in mice and rats (Martino-Andrade and Chahoud, 2010). In
addition, these compounds can also cause endometriosis in women,
adverse effects on the fetus, liver, kidneys, lungs, and heart, and are
potential carcinogens in humans (Singh and Li, 2011).
DEHP was observed to be more abundant in blood samples and urine
samples of people who were hospitalized due to the use of medical de­
vices. In addition, rural communities far from hospitals are exposed to
these compounds in the environment through packaged instant food
products or water. Based on the DEHP risk assessment in the work
environment by researchers, it is suggested that the work environment
should be managed to minimize exposure to below 5 mg m− 3 to protect
the health of workers (Kim, 2016; Rowdhwal and Chen, 2018). There­
fore, taking into account the widespread of DEHP and the potential
hazards to human health and the environment, the United States, Eu­
ropean Union, China and Japan have included it on the list of “priority
pollutants” that must be addressed immediately (Sampson and de korte,
2010; Zheng et al., 2014).
The method that has been developed previously is based on pre­
concentration techniques, such as liquid–liquid extraction, solid-phase
extraction (SPE), and micro-phase solid extraction (SPME), which was
then followed by separation methods, such as liquid or gas chromatog­
raphy combined with a mass spectrometry detection system (Khosh­
maram et al., 2018; Lirio et al., 2016; Wu et al., 2012). However, the
high cost because of the use of a large amount of solvent, complicated
sample handling, and sample complexity that can affect the efficiency
and selectivity of extraction, make this method unfeasible (Díaz de León-
Martínez et al., 2020). Thus, the development of a simpler DEHP anal­
ysis method with high efficiency and selectivity for the separation of
DEHP from various environmental matrices is urgently needed.
One of the currently promising methods for quantifying, deter­
mining, and extracting DEHP is solid-phase extraction based on molec­
ularly imprinted polymers (MIPs). Molecular printing involves the
synthesis of three-dimensional solid phases which have pores or cavities
intended to retain the desired molecule (Gallego-Gallegos et al., 2009).
The MIP is synthesized by using a template in the form of the desired
analyte, which provides a setting on the shape, orientation, and bond
that will be formed so that it can selectively maintain the structure after
the template is removed from the binding site. The release of this analyte
or template can leave an empty space to be re-occupied by the analyte or
closely related compounds (Díaz de León-Martínez et al., 2018). MIPs
have been used in DEHP removal studies because they exhibit low cost,
reversible adsorption and desorption, easy preparation technique, and
high thermal, mechanical and chemical stability (Huang et al., 2015).
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Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646
Magnetic nanoparticles (MNPs) are materials that have a super­
paramagnetic effect to be used for easy and rapid separation of liquid
and solid phases. The use of MNP as a “core” in the separation process
allows target molecules bound to the MIP surface to be easily separated
and collected by an external magnetic field without further processing,
such as centrifugation or filtration, which can simplify the subsequent
process and avoid secondary pollution caused by residual adsorbents
(Chen and Li, 2012). In addition, this method can be useful in selectively
recognizing template molecules in complex matrices and effectively
avoiding the disadvantages of conventional methods, such as size
mismatch, irregular morphology, template leakage, and low mass
transfer efficiency (Li et al., 2017). Therefore, combining MNP with MIP,
commonly called magnetic molecularly imprinted polymers (MMIPs),
can be a promising candidate for effective target pollutant removal and
selective separation processes. It is not surprising that currently this
method has attracted the attention of many researchers (Guo et al. 2019;
Pan et al. 2011; Zuo et al. 2019).
First, the preparation of MMIPs can be carried out by forming
magnetite using a coprecipitation technique between iron (II) chloride
(FeCl2⋅H2O) or iron (II) sulfate (FeSO4⋅7H2O) and iron (III) cloride
(FeCl3⋅6H2O) under basic conditions at 80–100 ◦ C (Kwaśniewska et al.,
2015). After the magnetite is formed, the surface modification of the
magnetite can be carried out by silanization or by adding a surfactant,
such as ethylene glycol or oleic acid to increase the amphoteric prop­
erties of the magnetite surface and enhance its interaction with polar
solutions. Next, the modified magnetite is polymerized using a template,
functional polymer, or cross-linking agent. The final step in MMIPs
preparation is the desorption of template molecules from the polymer
(Chen and Li, 2012).
The use of MMIPs in DEHP analysis has been carried out previously
through surface modification of magnetite by phenyltrimethoxysilane
(PTMS) as monomer and has shown good adsorption capacity and
selectivity towards DEHP. In addition, PEG has also been reported as a
surfactant for modifying magnetite (Li et al., 2017). Meanwhile, oleic
acid (OA) is a fatty acid that is widely used for grafting on adsorbents
and modification of hydrophobic materials which shows excellent
properties when applied as a surfactant to modify the magnetite surface
in the preparation of MMIPs (Ansari, 2017). However, to the best of our
knowledge, there are still no reports on the preparation of MMIPs using
oleic acid to remove DEHP from contaminated wastewater.
In this present work, novel magnetic molecularly imprinted poly­
mers (Fe3O4@MIPs) were prepared using Fe3O4 particles modified by
oleic acid as “core”, DEHP as a template, methacrylic acid (MAA) as
functional monomer, benzoyl peroxide (BPO) as initiator, and ethylene
glycol dimethacrylate (EGDMA) as crosslinkers. MMIPs were then
applied to the selective removal of DEHP from PVC plastic samples. The
adsorption behavior of DEHP on MMIPs was investigated, and the effect
of temperature, contact time and solution pH on adsorption was eval­
uated. The selectivity and reusability of adsorbents were also tested.
2. Materials and methods
2.1. Materials
Di(2-ethylhexyl)phthalate (DEHP) (>99.5%) and dibutylphthalate
(DBP) were obtained from Sigma Aldrich. Anhydrous iron(II) sulfate
(FeSO4⋅7H2O), iron (III) chloride (FeCl3⋅6H2O), methacrylic acid
(MAA), benzoyl peroxide (BPO), ethylene glycol dimethacrylate
(EGDMA), acetonitrile, oleic acid, polyvinylpyrrolidone (PVP), ethanol,
methanol, acetic acid glacial, sodium hydroxide, and acetonitrile were
purchased from Merck. All reagents used in the present study were of
analytical grade.
M. Ali Zulfikar et al.
Fig. 1. Schematic representation of the synthesis of the MMIPs for DEHP removal proposed in this work.
2.2. Synthesis of DEHP-imprinted polymer and non-imprinted polymer
2.2.1. Preparation of superparamagnetic Fe3O4 nanoparticles
As the “core” of the imprinted polymer, Fe3O4 was first synthesized
by the co-precipitation method [20]. FeSO4⋅7H2O (0.01 mol) and
FeCl3⋅6H2O (0.02 mol) were dissolved in 100 mL of water. The solution
was then stirred at 80 ◦ C in the presence of N2 gas and added by NaOH
(2 M) dropwise to produce Fe3O4 until the black precipitate was iden­
tified and easily separated using an external magnetic field. The
resulting Fe3O4 was then washed with demineralized water and ethanol
and dried in the oven at 60 ◦ C for 24 h. The Fe3O4 was then mixed with
oleic acid (OA) in a ratio of 1:1 (w/v) through sonication for 15 min to
coat the magnetite with a single surfactant layer of OA. The Fe3O4
nanoparticles were washed with demineralized water and ethanol,
stored in a desiccator to ensure complete solvent removal and then
characterized using FT-IR and SEM for structure investigation.
2.2.2. Synthesis of Fe3O4@MIPs (MMIPs) and Fe3O4@NIPs (MNIPs)
In this study, the magnetic molecularly imprinted polymers (MMIPs)
were synthesized over the Fe3O4 surface in the presence of DEHP as the
template molecule to form core@magnetic-MIPs using the precipitation
polymerization method. The pre-polymerization solution was prepared
by mixing DEHP (1 mmol), MAA (4 mmol), and the mixture of Fe3O4
nanoparticles (1 g) and EGDMA (20 mmol) in acetonitrile (30 mL)
through sonication for 30 min. In another beaker, 0.4 g of PVP was
shaken with 100 mL of ethanol (80%) under the presence of N2 gas at
400 rpm and then added to the pre-polymerization solution. During the
poplymerization reaction, BPO (150 mg) was added to the solution. The
polymerization was carried out in an oil bath (70 ◦ C) with continuous
stirring for 1 h. MMIPs named Fe3O4@MIPs as products were separated
from the solution using a magnetic field. The template molecule was
then removed by washing the polymer with MeOH:HOAc solution (9:1,
v/v) several times until no DEHP was detected. Magnetic non-
molecularly imprinted polymers (MNIPs) named Fe3O4@NIPs as con­
trol polymers were prepared by the same procedure in the absence of
DEHP. Both MMIPs and MNIPs were then dried in an oven at 60 ◦ C for
storage and use in the next step.
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Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646
2.3. Characterization
A TEM HT7700 microscope was used to obtain transmission electron
microscope (TEM) images of synthesized MMIPs. The morphology and
atomic composition of MNIPs and MMIPs were evaluated using a scan­
ning electron microscope (SEM)-EDX (SEM SU3500). Fourier transform
infrared (FT-IR) spectra were recorded using the FT-IR spectroscopy
(Jasco FTIR-4200) with a scanning range from 4000 cm− 1 to 400 cm− 1.
The magnetic properties of the samples within 1 T at room temperature
were tested by a vibrating sample magnetometer (VSM Oxford type
1.2H). In order to determine the concentration of DEHP in solution,
chromatography analysis was performed using HPLC-UV (Agilent 1261)
at a wavelength of 202 nm with C-18 Phenomenex as the stationary
phase and methanol:water (95:5, v/v) as the mobile phase, flow rate of
1.0 mL/min and injection volume of 20 μL.
2.4. Sorption studies
2.4.1. Effect of time on sorption
In order to evaluate DEHP binding kinetics by MMIPs, 10 mL of 20
ppm DEHP solution in methanol was added to six 25 mL glass flasks
containing 50 mg of MMIPs. At room temperature, the six mixtures were
then shaken (100 rpm) for 15, 30, 45, 60, 75, 90, 120, and 150 min.
Subsequently, the mixtures were filtered and analyzed by HPLC-UV
under the conditions mentioned in Section 2.3. The MNIPs were also
examined by the same procedure.
2.4.2. Effect of temperature on sorption
The effect of temperature on sorption was investigated by contacting
10 mL of 80 ppm, 100 ppm, 140 ppm, 200 ppm, 300 ppm and 500 ppm
DEHP solutions in methanol with 50 mg MMIPs. The solution was stirred
with a magnetic stirrer at a temperature of 25 ◦ C, 40 ◦ C and 55 ◦ C for 75
min using an incubator shaker. The MMIPs were then separated from the
DEHP solution using an external magnetic field. The DEHP concentra­
tion in the supernatant was measured by HPLC-UV as given in Section
2.3.
M. Ali Zulfikar et al.
Fig. 2. FT-IR spectra of Fe3O4 (a), modified Fe3O4 by OA (b), MNIPs (c), and MMIPs (d).
2.4.3. Adsorption capacity
To test the adsorption capacity, 50 mg of MMIPs was added to 10 mL
of solution with various concentrations of DEHP in methanol (20 ppm,
40 ppm, 60 ppm, 80 ppm, 100 ppm, 140 ppm, 200 ppm, 300 ppm, and
500 ppm). The mixtures were shaken on an orbital shaker (100 rpm) for
75 min at room temperature to facilitate the interaction between the
DEHP molecules and the active sites on the MMIPs. MNIPs were also
treated with the same procedure as controls. All solutions were analyzed
by HPLC-UV by the procedure as given in Section 2.3.
2.4.4. Selectivity test
The selectivity test was conducted by contacting MMIPs with DEHP
and another phthalate, i.e., dibutyl phthalate (DBP). 50 mg of MMIPs
were placed in a mixture of DEHP and DBP solution (10 mL) with initial
individual concentrations of 100 ppm. The mixtures were shaken for 75
min and then separated from the solution using a magnetic field. MNIPs
were also treated with the same procedure as controls. The concentra­
tion of DEHP and DBP in the supernatant were measured by HPLC-UV in
a similar manner to that described in Section 2.3.
2.5. Evaluation of reusability
The DEHP desorption capacity test was carried out with two kinds of
solvents, i.e., methanol and MeOH:HOAc (9:1, v/v). 50 mg of dried
MMIPs were shaken with 10 mL of solvent for 75 min at room temper­
ature. The MMIPs were then separated from the solution using a mag­
netic field. The concentration of DEHP in the supernatant was measured
by HPLC-UV to determine the amount of DEHP desorbed into the solu­
tion. MNIPs were also examined by the same procedure. The regenera­
tion test was performed by repeating the adsorption–desorption process
three times using the solvent, which showed the best results.
2.6. Removing DEHP from sample analysis
In this present study, the adsorption ability of MMIPs to remove
DEHP was evaluated using a PVC plastic extract solution. 1 g of PVC
plastic samples was extracted using 25 mL of methanol for 24 h and then
filtered using Whatman filter paper no. 42. 50 mg of MMIPs were then
contacted with 10 mL of the filtrate for a contact time of 75 min and then
separated from the solution using an external magnetic field. MMIPs
4
Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646
were then desorbed using 10 mL of methanol: acetic acid (9:1, v/v). The
solution was then analyzed using HPLC UV at a wavelength of 210 nm
using methanol: water (95:5, v/v) as the mobile phase and a Phenom­
enex C18 column as the stationary phase with a flow rate of 1 mL/min.
3. Results and discussion
3.1. Synthesis of MMIPs
The scheme of Fe3O4@MIPs synthesis is present in Fig. 1. Fe3O4
particles (magnetite) were first synthesized through co-precipitating of
iron(II) and iron(III) with the mol ratio of 1:2 in an alkaline condition
(Utami et al., 2021). Modification of the magnetite using oleic acid was
performed by a simple reaction to form a coordination interaction be­
tween the hydroxyl groups on the iron surface and the carboxylic groups
on the oleic acid. MMIPs were then prepared through polymerization on
the magnetite-oleic surface using methacrylic acid (MAA) as the
monomer, ethylene glycol dimethacrylate (EGDMA) as the crosslinking
agent, benzoyl peroxide (BPO) as initiator and DEHP as template
molecule. The number of crosslinkers involved in the reaction will
determine the morphology and binding sites of the MMIPs. The use of
too little amount of EGDMA will result in a more brittle and unstable
polymer due to the low degree of crosslinking. On the other hand, too
much EGDMA will result in a polymer with a low active site per unit
mass of polymer (Chen et al., 2011). Therefore, an appropriate amount
of EGDMA is required to produce MMIPs with the desired properties.
The ability of MMIPs to selectively recognize DEHP is due to the
interaction between MAA as a monomer and DEHP as a template
molecule. The interaction is formed from the presence of hydrogen
bonds between hydrogen on the carboxylate group of MAA and oxygen
on the ester group of DEHP. Another possible interaction is the presence
of weak van der Waals bonds along the DEHP alkyl chain with the co-
MAA EDGMA polymer. Some of these interactions can cause the tem­
plate molecules to be well embedded in the polymer matrix. In this
study, MMIPs were synthesized by a simple method that only took one
hour for the polymerization process. Desorption of DEHP from MMIPs
was also carried out easily because it used a magnetic field in its sepa­
ration. Compared to the previous methods, conventional methods for
MIP preparation require a polymerization time of 20–24 h and involve
the removal of template molecules in a complicated manner (Khan et al.,
M. Ali Zulfikar et al. Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646

Fig. 3. FT-IR spectra of DEHP (a), MMIPs before desorption (b), and MMIPs after desorption (c).

2008). In addition, the MMIPs synthesized by the method we proposed requires a grinding and sifting process prior to use. Such additional
in this study can also be used immediately after the template is removed. treatment may result in the destruction of certain imprinted sites
On the contrary to the MIP prepared by the conventional method, it (Shaikh et al., 2012). Therefore, the method that we used for the

Fig. 4. SEM image at magnification of 20.000x of Fe3O4 (a), MMIPs before desorption (b), MMIPs after desorption (c) and MNIPs (d).

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M. Ali Zulfikar et al. Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646

Table 1 the template molecule was released from the MMIPs, it was found that
The composition of the elements contained in MNIP, MMIP before and after there were specific for the shape, size and bonding side of DEHP. The
desorption. void size in MMIPs after leaching also has a bigger size and more uni­
Polymer %C %O %Fe form than in MNIPs (Fig. 4(c)).
MNIPs 69.91 25.16 4.92
EDX analysis was conducted to determine the atomic composition of
MMIPs before desorption 69.95 25.18 5.27 the polymer constituents. The results of the analysis of atomic compo­
MMIPs after desorption 72.32 25.21 2.48 sition on MNIPs, MMIPs before the release of DEHP, and MMIP after the
release of DEHP can be seen in Table 1.
The EDX analysis results showed no significant difference in the
preparation of MMIPs is more manageable and can overcome the
percentage of carbon and oxygen atoms between MNIPs and MMIPs
weaknesses that exist in the conventional method.
before desorption. However, there was a decrease in the percentage of
iron atoms up to 2.48% (w/w) for MMIPs after desorption due to the low
resistance of the polymer to the solvent used, i.e., MeOH:HOAc (9:1, v/
3.2. Characterizations
v). These results indicate that the polymer can be separated from
magnetite, and then the iron in magnetite can dissolve in MeOH:HOAc,
3.2.1. FT-IR spectra
which causes the low value of iron content in MMIPs after desorption,
Fig. 2 exhibits the FT-IR spectrogram of Fe3O4, modified Fe3O4 by
which is also consistent with the FT-IR characterization of MMIPs after
OA, MNIPs and MMIPs. The absorption peak at 586 cm− 1 corresponds to
the release of the template molecule showing a low intensity of Fe-O
the typical vibration of the Fe-O at the tetrahedral and octahedral sites of
peaks.
the Fe3O4 spinel-type structure, which is also presented in MNIPs and
MMIPs spectra. The strong absorption peaks at 1728 cm− 1 and 1159
3.2.3. TEM
cm− 1 in the spectrum in Fig. 2(c) and Fig. 2(d) represent the C– –O
The morphological structure of MMIPs was also evaluated by TEM
stretching and C–O vibrations of methacrylic acid. The peak at 2954
with magnifications of 20,000× and 100,000× (Fig. 5). The results show
cm− 1 is assigned to the C–H vibration of oleic acid. The broad peak at
that MMIPs have a magnetite core with a regular spherical shape coated
3468 cm− 1 in the spectra of MNIPs and MMIPs indicates the presence of
with polymer. Fig. 5(b) indicates that MMIPs covered on the Fe3O4
O–H bonds originating from the template molecule and the monomer.
surface, displaying an apparent core–shell structure. The thickness of the
This peak is also seen in Fig. 2(b), which shows the presence of an OH
shell has various sizes, with an average size below 100 nm. Based on the
group on the surface of Fe3O4 that is bound to oleic acid.
distribution measurement, some MMIPs are 50–79 nm, and 19% MMIPs
The MMIPs after desorption were also characterized using FT-IR
are above 100 nm. The various sizes of MMIPs are due to the different
spectroscopy to ensure that DEHP was removed from MMIPs. The FT-
sizes of Fe3O4 as the polymer core.
IR spectra of DEHP, MMIPs before desorption and MMIPs after desorp­
tion can be seen in Fig. 3. The presence of weak absorption peaks at 709
3.2.4. Zeta potential
cm− 1 (pattern of out-of-plane C–H bending bands which are charac­
The zeta potential analysis of MMIPs after desorption and MNIPs was
teristic of aromatic substitution pattern), 1072 cm− 1 and 1155 cm− 1 (O-
carried out to determine the surface charge of the polymer. The analysis
CH3 substituted aromatic group of DEHP) in the spectrum of MMIPs
was repeated three times using demineralized water at pH 5, which
before desorption (Fig. 3(b)) corresponds to the typical peaks of aro­
corresponded to the pH of the solvent in the adsorption process. The
matic derivatives, proving the presence of DEHP in MMIP particles
results showed that the surface charge of MMIPs after desorption
(Hankett et al., 2014). However, these peaks are not seen in Fig. 3(c),
(− 72.4 mV) was more negative than that of MNIPs (− 24.6 mV) due to
indicating that DEHP has been desorbed from MMIPs. The intensity of
the tendency of DEHP to be hydrolyzed at pH below 7 to produce
the benzene absorption peak in Fig. 3(b) is smaller than that in Fig. 3(a)
phthalic acid. The carbonyl group in phthalic acid as a result of the
due to the low concentration of DEHP in MMIPs.
hydrolysis reaction is nucleophilic and will react with hydrogen ions in
solution to produce positively charged species (Baharin et al., 2016).
3.2.2. SEM
This process causes the positively charged DEHP to have a greater
The morphological structure of Fe3O4, MNIPs and MMIPs can be
attractive force on the MMIPs than the MNIPs. Therefore, after the
evaluated by performing SEM measurements. SEM images of Fe3O4,
release of the DEHP molecule, the MMIPs will be more negatively
MMIP and MNIP are shown in Fig. 4. The image shows that after
charged than the MNIPs.
desorption, MMIPs have a bigger void size than before leaching. After

Fig. 5. TEM image of MMIPs at magnification of 20,000× (a) and 10,000× (b).

6
M. Ali Zulfikar et al. Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646

80

60

40

20
M (emu/g)

0
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
-20

-40
magnetit
-60 MMIP

-80
H (T)
Fig. 6. Magnetization curve of magnetite and MMIP.

1.2

1.0

0.8
Q (mg/g)

MMIP
0.6 MNIP

0.4

0.2

0.0
0 30 60 90 120 150
t (min)
Fig. 7. Effects of contact time to DEHP adsorption.

3.2.5. VSM analysis
The synthesized MMIPs and Fe3O4 were characterized using VSM at
room temperature to investigate the magnetic properties of the polymer.
The hysteresis curve of the magnetization measurement (M) against the
external magnetic field (H) is shown in Fig. 6. The measurement results
indicate that the saturation magnetization of Fe3O4 and MMIPs are
62.35 and 39.92 emu− 1, respectively. The saturation magnetization of
MMIPs is weaker than the magnetite due to the presence of a molecu­
larly imprinted shell on the surface of Fe3O4 in MMIPs, which prevents
its magnetic responsiveness. However, MMIPs still have strong magnetic
properties at room temperature, making them potent effective separa­
tion carriers. The measurement results also show that Fe3O4 and MMIPs
have a high saturation magnetization when affected by an external
magnetic field and show zero average coercivity with no magnetic
remanence when not affected by an external magnetic field so that both
materials are classified as superparamagnetic (Koplovitz et al., 2019).

7
M. Ali Zulfikar et al. Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646

Table 2
Parameter of MMIPs adsorption kinetic
log(qe − qt ) = lnqe − k1 t (1)

Polymer Model k Qe R2 where qt and qe (mg g− 1) are the binding amounts of MMIPs and MNIPs
MMIPs Pseudo-first order -2
5.91 × 10 min − 1
0.18 mg/ 0.9114 at contact time (t) and the equilibrium adsorption capacity of MMIPs
g and MNIPs, respectively, k1 (min− 1) is the pseudo-first-order kinetic
-1 − 1
Pseudo-second 7.699 × 10 g mg min 1.3 mg/g 0.9898
-1 constant (Yuh-Shan, 2004). The linear equation of the pseudo-second-
order
MNIPs Pseudo-first order 3.57 × 10-2 min− 1
0.66 mg/ 0.7288 order kinetic model is expressed as follows.
g
t 1 t
Pseudo-second 3.54 × 10-2 g mg− 1
0.58 mg/ 0.818 = + (2)
order min− 1 g qt (k2 q2e ) qe

where k2 (g mg− 1 min− 1) represents the second-order kinetic rate con­

3.3. Molecular recognition properties
3.3.1. Kinetic of adsorption
The adsorptive ability and adsorption balance were measured by
adsorption kinetics experiments. The adsorption kinetics of MMIPs to
DEHP was determined by contacting 50 mg of MMIPs in a 20 ppm DEHP
solution for 15, 30, 45, 60, 75, 90, 120 and 150 min. The adsorption
kinetics of DEHP solution onto MMIPs and MNIP is shown in Fig. 7.
Based on Fig. 7, the adsorption capacity of MMIPs increases rapidly
in the first 60 min, and then the curve tends to become relatively flat and
reaches the adsorption equilibrium at about 75 min. Slightly different
behaviour with the same adsorption contact time in equilibrium was
observed for the adsorption onto MNIPs. The shallow voids on the sur­
face of MMIPs and MNIPs are favourable for rapid adsorption of DEHP.
However, when the void reaches saturation, the mass transfer process is
inhibited, which causes a decrease in the adsorption rate. According to
the curve, it can also be seen that the number of active sites can affect the
adsorption rate, due to MMIPs have more active sites than MNIPs,
making MMIPs have a better adsorption rate and greater adsorption
capacity than MNIPs.
In this study, two adsorption kinetic models, pseudo-first-order and
pseudo-second-order kinetic models, were used to investigate the dy­
namic adsorption process of MMIPs and MNIPs. The linear equation of
the pseudo-first-order model can be described as:
stant, and t is the time (minutes) (Ho and McKay, 1999).
The kinetic parameter data are shown in Table 2. The results show
that the correlation coefficient of the pseudo-second-order model (R2 =
0.9898) is greater than that of the pseudo-first-order model (R2 =
0.9114), indicating that the pseudo-second-order model is a better fit to
explain the adsorption process of MMIPs.
The adsorption mechanism of DEHP solution by the imprinted
polymer consists of four steps as follows. The diffusion of solutes from
the bulk phase to the boundary layer around the DEHP molecules (first
stage); the diffusion from the boundary layer to the MMIPs or MNIPs
surface (second stage); diffusion from the surface to the inner side of the
imprinted polymer (third stage); and the adsorption process consisting
of chemical-physical adsorption, ion exchange, precipitation or complex
formation (fourth stage) (Allen et al., 1999). The first, second and fourth
stages will determine the rate of the adsorption process, while the third
stage is assumed to run very fast. The mechanism of the pseudo-second-
order adsorption process is explained with the assumption that a
chemical adsorption process is a determinant of the reaction rate that
includes intervalence forces or electron exchange between the adsorbent
and the adsorbate. According to these results, the step that acts as a
determinant of the rate of DEHP adsorption onto MMIPs is the fourth
stage with the slowest adsorption process.
3.3.2. Isotherm of adsorption
In this study, the adsorption isotherm was analyzed to evaluate the

18

16

14

12

10
Q (mg/g)

8 MMIP

6 MNIP

0
0 100 200 300 400 500
Ce (ppm)
Fig. 8. Isotherm adsorption curve of DEHP onto MMIPs and MNIPs.

8
M. Ali Zulfikar et al. Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646

Table 3 amount of DEHP adsorbed per unit weight of adsorbent (mg g− 1), KL is
Langmuir and Freundlich isotherm model data of MMIPs and MNIPs the Langmuir constant (L mg− 1), qm is the maximum adsorption capacity
Polymer Langmuir Freundlich (mg g− 1), and KF (mg1-n Ln g− 1) and n are Freundlich’s constants.
2 Table 3 shows the Langmuir and Freundlich adsorption isotherm
KL (L Qmaks (mg R KF (mg1-n nF R2
mg− 1) g− 1) Ln g− 1) modelling data on MMIPs and MNIPs. The table shows that the corre­
lation coefficient value of the Langmuir adsorption isotherm model (R2
MMIPs 0.0064 17.21 0.9796 0.1856 0.7714 0.9693
MNIPs 0.0019 0.82 0.6437 0.0053 0.8589 0.602
= 0.9796) is greater than the Freundlich adsorption isotherm model (R2
= 0.9693). Thus, the Langmuir isotherm model is more suitable to
explain the DEHP adsorption process by MMIPs.
equilibrium relationship between the concentration of DEHP remaining The Langmuir adsorption model explains that the adsorption of
in solution and the amount of DEHP adsorbed per unit mass of the template molecules occurs on the monolayer (single-layer) surface of the
adsorbent in equilibrium at a constant temperature. The adsorption adsorbent with a maximum adsorption capacity of MMIP of 17.21 mg
capacity of DEHP onto the adsorbent was studied by contacting 50 mg of g− 1. The imprinting factor (IF) value is known by comparing the value of
MMIPs or MNIPs at various concentrations of DEHP solutions in the the Langmuir constant on the MMIPs and MNIPs values. The IF value of
range of 40 ppm to 500 ppm for 75 min, and the results are shown in MMIPs is 3.37 (>1), which indicates that MMIPs have a better adsorp­
Fig. 8. tion capacity than MNIPs. The presence of specific binding sites on the
Fig. 8 represents that the adsorption capacity of MMIPs increased surface of MMIPs will increase the adsorption capacity of MMIPs to
rapidly with increasing initial concentration of DEHP solution. At higher DEHP.
initial concentrations over 200 ppm, the adsorption capacity values
tended to be stable. In addition, compared to MNIPs, MMIPs have a 3.3.3. Thermodynamics of adsorption
higher adsorption capacity which is primarily due to the specific The thermodynamics of adsorption can be determined by studying
adsorption of the voids in the polymer. The adsorption of DEHP onto the effect of temperature on the adsorption capacity of MMIPs. Based on
MNIPs mainly depends on the polar groups on the MNIPs surface. These Fig. 9, it was observed that the adsorption capacity of MMIPs increases
nonspecific binding sites in MNIPs will cause weak adsorption ability. with increasing DEHP concentration in equilibrium (Ce) but decreases
On the other hand, the adsorption of DEHP onto MMIPs was due to the along with the increasing temperature due to the instability of hydrogen
presence of 3D voids equipped with the spatial structure of DEHP. bonds at high temperatures. The thermodynamic adsorption studies
Therefore, MMIPs have a “memory function” on the template and strong show that the best adsorption capacity exists around the physiological
selective adsorption ability. temperature, indicating potential applications for samples contained in
Langmuir and Freundlich adsorption isotherm models were used to the environment without further heating.
evaluate the experimental data and described by the following equation To evaluate the thermodynamic ability of adsorption, the standard
(Dąbrowski, 2001; Boparai et al., 2011). free-energy change (△Go), the standard enthalpy change (△Ho), and
the standard entropy change (△So) were calculated from the
1 1 1
= + (Langmuir isotherm) temperature-dependent adsorption isotherms based on the following
qe (KL qm )Ce qm
equation:
(logCe ) (5)
◦
logqe = logKF + (Freundlich isotherm) ΔG = − RTlnK
n
◦ ◦

where Ce is the adsorbate concentration at equilibrium (mg L-1), qe is the

ΔH ΔS
lnK = − + (6)
(RT) R

18

15

12
298 K
Q (mg/g)

9
313 K

6 328 K

0
0 100 200 300 400 500
Ce (mg/L)
Fig. 9. Effects of temperature towards adsorption capacity of MMIPs.

9
M. Ali Zulfikar et al. Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646

Table 4 negative and increase with increasing temperature, indicating that the
Parameter data of MMIPs adsorption thermodynamics adsorption reaction occurs spontaneously at various temperatures.
T (K) K ΔH◦ (kJ mol− 1) ΔS◦ (J mol-1K− 1) ΔG◦ (kJ mol− 1) Generally, when physical adsorption occurs, the value of ΔG◦ is in the
5 range of 0 to 20 kJ mol− 1. As for chemical adsorption, the value of ΔG◦
298 2.05 × 10 − 82.17 − 175.2 − 29.96
313 2.72 × 104 − 27.33 ranges from 80 to 400 kJ mol− 1. Therefore, it can be concluded that the
328 1.0 × 104 − 24.71 adsorption of DEHP to MMIPs in this study was controlled by phys­
isorption (Bayramoglua et al., 2016).

where ΔG◦ is the change in Gibbs free energy (kJ mol− 1), R is the uni­
3.4. Selectivity of MMIPs to analogous compounds
versal gas constant (8.314 J K-1mol− 1), T is the temperature (K), K is the
thermodynamic constant (L mg− 1), ΔH◦ is the standard enthalpy change
The adsorption selectivity of MMIPs was determined by comparing
(kJ mol− 1), ΔS◦ is the standard entropy change (J.mol-1K− 1). Table 4
the adsorption capacity of MMIPs and MNIPs for DEHP and its structural
shows the thermodynamic parameter data for MMIPs adsorption.
analogue compounds. In this study, the selectivity of DEHP to MMIP was
Based on Table 4, it is known that ΔH◦ is negative, which indicates
evaluated using dibutyl phthalate (DBP) as the analogue compound
the reaction is exothermic. The negative value of ΔS◦ suggests a decrease
(Fig. 10). Both compounds have the same main framework, namely the
in randomness at the adsorption-solution interface in the adsorption
benzene diester group. However, DEHP has diethyl and hexyl chains
process, and it implies that the adsorption process of DEHP onto MMIPs
which are longer than the alkyl chains in DBP.
is enthalpically driven (Kim and Guiochon, 2005). The ΔG◦ values are
The binding efficiency of MMIPs and MNIPs was evaluated through a

Fig. 10. Structure of di-2-ethylhexylphthtalate (a) and dibutylphthalate (b).

3.50

3.03
3.00

2.50

2.00
Q (mg/g)

DEHP

1.50 DBP

1.00
0.75

0.44
0.50 0.32

0.00
MIP NIP

Fig. 11. Selectivity of MMIPs and MNIPs toward DEHP and DBP.

10
M. Ali Zulfikar et al. Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646

120
MeOH MeOH:HOAc (9:1)
100 98.42 96.69

80
% desorption

60

40
31.80
27.25
20

0
MMIP MNIP
Fig. 12. Percentage of desorption of MMIPs and MNIPs.

18

16 15.29
14.04
14 13.57

12
Q (mg/g)

10
MMIP
8 MNIP

2
0.63 0.59 0.00
0
1 2 3
Fig. 13. Regeneration of MMIPs and MNIPs using MeOH:HOAc (9:1, v/v).

non-competitive binding study using an initial concentration of DEHP or
DBP of 100 mg L-1, and the graph is shown in Fig. 11. The figure shows
that the adsorption capacity of MMIPs to DEHP (Q = 3.03 mg g− 1) was
much higher than DBP (Q = 0.75 mg g− 1). The graph also shows that
MMIPs show better selectivity to DEHP than MNIPs. The presence of a
complementary site for DEHP in MMIPs provides selectivity for this
molecule. DBP is an analogue molecule with a smaller size and has no
branches in its alkyl chain. These characteristics can reduce the number
of interaction sites with functional groups designed for DEHP in the
MMIPs cavity, and cause DBP to be poorly fitted into it, leading to lower
adsorption efficiency for this molecule (Zulfikar et al., 2017).
3.5. Reusability of MMIP
The desorption capacity test was conducted using two solvents
(methanol and MeOH:HOAc (9:1, v/v)). Based on Fig. 12, both MMIPs
and MNIPs showed much better desorption capacity (98.42% and
96.69%) using MeOH:HOAc (9:1, v/v). Meanwhile, desorption using
methanol only gave the percentage of desorption for MMIPs and MNIPs
of 27.25% and 31.80%, respectively. The data indicates that acetic acid
plays a role in the process of releasing DEHP from the polymer through
the interaction of hydrogen bonds between acetic acid and DEHP, which
is stronger than the van der Waals interaction between DEHP and the
polymer surface.
Regeneration of the polymer is also necessary to identify how often

11
M. Ali Zulfikar et al. Environmental Nanotechnology, Monitoring & Management 17 (2022) 100646

Fig. 14. Chromatogram of the sample solution before contacting with MMIPs (a) and after contacting with MMIPs (b).

the polymer can be reused. The same amount of MMIPs and MNIPs were
Table 5
used in the adsorption–desorption process, and it was carried out three
Validation parameters of DEHP analysis in PVC plastic samples
times using MeOH:HOAc (9:1, v/v). Based on Fig. 13, it was observed
that the adsorption capacity of MMIPs decreased by 11.2% after three Validation parameters DEHP

times polymer regeneration. Meanwhile, MNIPs can only be used a − 1

Linear range (μg. mL ) 2–10
maximum of two times for regeneration. The decrease in adsorption Linearity (r2) 0.9989
Slope (a) 0.1153
capacity in MMIPs and MNIPs may be due to the changes in the number
Intercept (b) 0.031
of active sites on the surface of the polymer void because of washing, LOD (μg. mL− 1) 0.395
which indicated by the presence of black magnetite particles that are not LOQ (μg. mL− 1) 1.197
coated with the polymer during washing. In addition, some of the Intra-assay precision (% RSD) 4.655
polymer voids may have been filled with template molecules and are Recovery (%) 91.03–99.68

difficult to desorb, thus affecting the subsequent adsorption process

(Yuan et al., 2018).
Table 6
Maximum adsorption capacity values of DEHP onto various adsorbents.
3.6. Application of MMIP
Adsorbent(s) qm (mg/g) References

In order to confirm that MMIPs could be competent for removing Oxidized corncob biochar 11.8–16.16 (Salam et al., 2021)
DEHP from the wastewater, the adsorption test of MMIPs was conducted Multi-walled CNT based MMIP 1.38 (Deng et al., 2021)
Reduced graphene oxide 10.9 (Yunusa et al., 2021)
by contacting 50 mg of MMIPs with 10 mL of PVC plastic samples so­
MMIP with MPS-SiO2-Fe3O4 microsphere 5.36 (Yuan et al., 2018)
lution. MMIPs were then desorbed using 10 mL of MeOH:acetic acid C8-modified magnetic graphene oxide 2.50 (Wang et al., 2018)
(9:1). The chromatogram of the sample solution before and after con­ Cellulose nanofibers 14.8 (Makzoom et al.,
tacting by MMIPs can be seen in Fig. 14. Based on the chromatogram, 2017)
the DEHP adsorption process by MMIPs succeeded in reducing the ma­ MIPMs by pickering emulsion 1.75 (Fan et al., 2016)
polymerization
trix disturbance in the sample. The matrix in the sample after contacting Polyaniline montmorillonite clay composite 6.53 (Qureshi et al.,
with MMIPs the desorption process can still be seen at its peak at 2.99 2016)
min. However, the peak area on the chromatogram was much reduced, Surface imprinted polymers with modified 16.08 (Yang et al., 2015)
indicating the role of adsorbent selectivity on DEHP. The presence of silica gel
Biofilms 0.162 (Cao et al., 2014)
high and wide peaks on the chromatogram (retention time = 1.79 min)
MIP with methacrylamide/MBAm 9.986 (Shaikh et al., 2012)
was the peak of methanol: acetic acid (9:1) as a desorption solvent. Seaweed biomass 5.68 (Chan et al., 2004)
Based on the chromatogram, it can be shown that the difference in Fe3O4@MIPs 17.21 this study
DEHP retention time in the sample before desorption is 3.6 min and after
desorption is 3.4 min due to differences in the use of solvents for the
sample and those used in the desorption process. To investigate and summarized in Table 5. Linearity was achieved in the range of 2–10 μg
validate the analytical method, a series of analytical performance mL− 1 with a linearity of 0.9989.
characteristics taking into account linearity, limit of detection (LOD), The detection was carried out three times for each sample and the
limit of quantification (LOQ), and recovery were performed and mean percentage of recovery found from the test varied between 91.03

12
M. Ali Zulfikar et al.
and 99.68%. In order to determine the amount of DEHP contained in the
PVC plastic samples, validation method was performed and the results
are summarized in Table 5. From these data, the DEHP concentration in
the PVC plastic sample was 6.2453 μg mL− 1.
3.7. MMIPs adsorption capacity compared to various adsorbents
In this study, to find out how efficiently MMIPs used as adsorbents to
remove DEHP from contaminated sample, the maximum adsorption
capacity (qmax) of MMIPs was compared with various previously re­
ported adsorbents. Table 6 indicates that the adsorption capacity of
MMIP synthesized in this study (Fe3O4@MIPs) showed a higher value
when compared to various adsorbents that have been reported to be
used for DEHP removal. Therefore, it can be concluded that MMIPs can
be considered as promising adsorbents to effectively remove DEHP from
a contaminated sample.
4. Conclusion
Novel magnetic molecularly imprinted polymers (MMIPs) selective
for di-(2-ethylhexyl) phthalate (DEHP) in PVC plastic sample were
successfully synthesized using methacrylic acid as functional monomer,
Fe3O4 modified by oleic acid as magnetic “core”, and ethylene glycol
dimethacrylate as a crosslinking agent. The synthesized MMIPs
(Fe3O4@MIPs) were found porous in nature with superparamagnetic
properties. The MMIPs also showed good adsorption capacity over
DEHP with an adsorption capacity value of 17.21 mg g− 1 and an
imprinting factor (IF) value of 3.37. Moreover, the MMIPs followed the
Langmuir isotherm model and fitted well to a pseudo-second-order ki­
netic model with ΔHo of − 82.17 kJ mol− 1. The MMIPs can be repeatedly
used with a desorption percentage of 98.42 % and a decrease in
adsorption capacity of 11.2% after three times regenerations. Based on
MMIPs selectivity test on PVC plastic samples, it was known that the
MMIPs could reduce the matrixes effect with the recovery percentage
around 91.03–99.68%.
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.
Acknowledgement
The author is very grateful to the Director General of Higher Edu­
cation, Ministry of Education and Culture for the financial support of
this research study through the World Class Research 2020/2021.
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