Environmental Pollution 158 (2010) 2317e2323

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Synthesis of core-shell magnetic molecular imprinted polymer by the surface

RAFT polymerization for the fast and selective removal of endocrine disrupting
chemicals from aqueous solutions
Ying Li a, Xin Li a, *, Jia Chu a, Cunku Dong a, Jingyao Qi b, Yixing Yuan b
a
b

Department of Chemistry, Harbin Institute of Technology, Harbin 150090, China

School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China

Magnetic molecular imprinted polymers have potential as adsorptive materials in water treatment.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 23 October 2009
Received in revised form
3 February 2010
Accepted 4 February 2010

In this study, we present a general protocol for the making of surface-imprinted core-shell magnetic
beads via reversible addition-fragmentation chain transfer (RAFT) polymerization using RAFT agent
functionalized iron oxide nanoparticles as the chain transfer agent. The resulting composites were
characterized by X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) analysis, thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), and scanning electron microscopy (SEM)
and transmission electron microscopy (TEM). The surface-imprinted magnetic beads were demonstrated
with a homogeneous polymer lms (thickness of about 22 nm), spherical shape, and exhibited magnetic
property (Ms 0.41 mA m2 g1) and thermal stability. Rebinding experiments were carried out to
determine the specic binding capacity and selective recognition. The as-synthesized surface-imprinted
core-shell magnetic beads showed outstanding afnity and selectivity towards bisphenol A over structurally related compounds, and easily reach the magnetic separation under an external magnetic eld. In
addition, the resulting composites reusability without obviously deterioration in performance was
demonstrated at least ve repeated cycles.
2010 Elsevier Ltd. All rights reserved.

Keywords:
Endocrine disrupting chemicals
Molecularly imprinted polymer
Iron oxide
Removal

1. Introduction
Endocrine disrupting chemicals (EDCs) are chemicals with the
potential to elicit negative effects on the endocrine systems of
humans and wildlife. Over the past few decades, the EDCs presented in the environment have received considerable attention in
the scientic and public community (Martin-Skilton et al., 2006;
Matthiessen and Johnson, 2007). It has been shown that EDCs
cannot be completely eliminated by conventional treatment
methods in complex environmental matrices, resulting in the
formation of by-products with even a higher endocrine disrupting
action (Korshin et al., 2006; Gogate and Pandit, 2004; Stackelberg
et al., 2004). For the removal and perhaps recovery of the EDCs
from the environment, it is desirable to use adsorptive materials,
which have high recognition and selectivity towards the EDCs,
together with rapid sorption kinetics.

* Corresponding author. Tel.: 86 451 86282153; fax: 86 451 86418750.

E-mail address: lixin@hit.edu.cn (X. Li).
0269-7491/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2010.02.007

Molecularly imprinted polymers (MIPs) are a new kind of smart

materials that display remarkable recognition properties (Piletsky
et al., 2001). Nowadays, molecular imprinting is a widely used
method for the preparation of tailor-made materials with a high
recognition towards a target molecule, normally the template using
which the material was prepared (Bolisay et al., 2006; Haupt and
Mosbach, 2000; Henry et al., 2005; Janiak and Konas, 2007;
Karim et al., 2005; Mahony et al., 2005; Spivak, 2005).
Selective recognition and removal of EDCs from aqueous solution using MIPs have been recently demonstrated (Alexiadou et al.,
2008; Mathieu et al., 2007; Meng et al., 2005). Conventionally, MIPs
are synthesized by using the free-radical polymerization technique.
However, the rate of chain propagation in the free-radical polymerization process is difcult to control, and the resultant polymer
generally has a broad size distribution due to side reactions. While
such MIPs can exhibit high afnity and selectivity, their adsorptive
capacity and accessibility to the adsorptive sites for a target
molecule are in general poor (Chen et al., 1999). To solve these
problems, different living/control radical polymerization techniques have been developed. Amongst, the reversible additionfragmentation chain transfer (RAFT) polymerization, rst reported

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Y. Li et al. / Environmental Pollution 158 (2010) 2317e2323

by Rizzardo and co-workers (Chiefari et al., 1998), is a most

promising method. The RAFT polymerization method allows one to
control the polymerization of a wide range of monomers without
using metal catalysts under mild polymerization conditions. In
addition, the resultant polymer obtained by RAFT polymerization is
end-capped by the moieties derived from the RAFT agent. As
a result, the functional groups can be easily introduced into the
chain ends of the polymer by adjusting the structure of the RAFT
agent used in the RAFT process (Lowe and McCormick, 2007).
Recently, the RAFT polymerization technique has been extensively
used to prepare MIPs (Lu et al., 2007; Southard et al., 2007). Thin
lms of molecularly imprinted polymers that combine covalent
immobilization of azo initiators with RAFT-mediated living radical
polymerization on mesoporous silica beads have been reported
(Titirici and Sellergren, 2006).
Separation of a solid from an aqueous solution represents a huge
issue in engineering aspect. A great deal of recent research effort
has been made at magnetic solids, which can be easily separated
from the medium simply by applying an external magnetic eld.
Recently, the preparation of magnetic MIP nanowires has been
described (Li et al., 2006). Nanopore alumina was used as template.
The magnetic MIP nanowires displayed excellent properties for
theophylline. Bovine serum albumin surface-imprinted submicrometer particles (500e600 nm) with magnetic susceptibilities
prepared by using miniemulsion polymerization method have been
reported (Tan et al., 2008). More recently, we have developed
a general approach to rational design of MIPs for the determination
of toxic pollutants from extreme environments (Li et al., 2009a,b).
In this work, superparamagnetic core-shell beads with magnetic
iron oxide covered with silica as the core and MIP as the shell were
prepared using the suspension polymerization method. The
recognition and removal efciency of the beads for EDCs from
aqueous environment was investigated. Bisphenol A (BPA) [2,2-bis
(4-hydroxyphenyl) propane] was chosen as a model contaminant
for it is considered as a highly active estrogen frequently present in
the environment (Chen et al., 2007; Hu et al., 2002; Suzuki et al.,
2004).The preparation of the surface-imprinted core-shell
magnetic beads is schematically illustrated in Scheme 1. It involves
a couple of steps, including the synthesis of Fe3O4 microspheres,
deposition of a thin layer of silica on the sphere surfaces, MIPfunctionalized onto the silica surface, and nal extraction of BPA
and generation of the recognition site. The as-synthesized surfaceimprinted core-shell magnetic beads showed a high afnity,
selectivity, and easy separation behavior.
2. Experiment section
2.1. Materials
Ultra-dried tetrahydrofuran (THF), phenylmagnesium bromide and 4-(chloromethyl)phenyltrichlorosilane were obtained from the J&K Chemical Ltd. Acrylamide (AAm) was provided by the Shanpu Chemical Co., Ltd. (Shanghai, China).
Tetraethyl Orthosilicate (TEOS) was purchased from the Bodi Chemical Reagent Co.,
Ltd. (Tianjin, China). 4,40 -Sulfonyldiphenol, BPA, phenol, azobisisobutyronitrile
(AIBN) and divinylbenzene (DVB) were purchased from the Guangfu Chemical
Industry (Tianjin, China). Chromatographically pure toluene was obtained from the
Kermel Chemical Reagent Co., Ltd. All other chemicals were of analytical grade and
used as received. For practical water samples, tap water was taken from the water
supply system on our campus. The characterization of the drinking water sample
was expressed as follows: pH 6.80, turbidity 0.35 (NTU), and total organic
carbon (TOC) 2.01 mg L1.
2.2. Preparation of Fe3O4@SiO2 microspheres
Iron oxide nanoparticles were rst synthesized by solvothermal reduction
method (Deng et al., 2005). Fe3O4@SiO2 microspheres were prepared according to
the method reported with minor modication (Fang et al., 2008). Typically, 2 mL
Fe3O4 water-based magnetic uid (40 mg mL1) was dispersed in 60 mL ethanol and
10 mL of highly puried water by sonication for 15 min, followed by the addition of

1.0 mL ammonium hydroxide (25 wt%) and 2.0 mL TEOS sequentially. The mixture
was reacted for 24 h at the room temperature under a continuous stirring. The
resultant product was collected by an external magnetic eld, and rinsed six times
with ethanol and highly puried water, respectively. Finally, the Fe3O4@SiO2
microspheres obtained were dried under vacuum at 60  C for 24 h.
2.3. Synthesis of 4-(chloromethyl)-phenyltrichlorosilane functionalized Fe3O4@SiO2
microspheres (Fe3O4@SiO2-Cl)
To prepare the Fe3O4@SiO2-Cl, 2.0 g of Fe3O4@SiO2 was dispersed in a solution of
4.0 mL 4-(chloromethyl) phenyltrichlorosilane in 55 mL of anhydrous toluene. After
ultrasonic treatment for 20 min, a solution of triethylamine (2.0 mL) in anhydrous
toluene (5.0 mL) was slowly added to the former mixture. After the addition was
complete, the resulting mixture was heated at reux for 24 h under nitrogen
protection. The product was washed with methyl alcohol for ve times. Finally, the
Fe3O4@SiO2-Cl obtained was dried under vacuum at 60  C for 24 h.
2.4. Synthesis of Fe3O4@SiO2-RAFT agent
14.5 mL phenylmagnesium bromide was dispersed in 130 mL ultra-dried THF, and
reacted with 3.5 mL carbon disulde at 45  C for 2 h. The reaction mixture was then
added 0.5 g Fe3O4@SiO2-Cl and kept at 65  C for 72 h under nitrogen protection. After
polymerization was complete, the resulting products (Fe3O4@SiO2-RAFT agent) were
washed with methanol and acetone, separately, for 5 times, and the nanoparticles
were dried under vacuum at 60  C for 24 h.
2.5. Preparation of MIP nano-lm on the surface of Fe3O4@SiO2-RAFT (Fe3O4@SiO2MIP)
6 mmol AAm, 20 mmol DVB and 220 mg Fe3O4@SiO2-RAFT agent were dispersed
into a 10 mL chloroform solution of BPA (1 mmol). After sealing, shaking, and
purging the mixture with nitrogen, a 5 mL acetonitrile solution of 50 mg AIBN
(initiator) were added into this suspension with glass syringe. The resultant mixture
was stirred at 60  C for 24 h under nitrogen protection, and then separately washed
several times with chloroform, methanol-acetic acid (9:1, v/v) solution and acetone
until the template was not detected. Finally, the resultant polymer was dried under
vacuum at 60  C for 24 h. As a reference, non-imprinted polymer coated magnetic
nanoparticles (Fe3O4@SiO2-NIP) was prepared without the template, was also
prepared in parallel with the Fe3O4@SiO2-MIP by using the same synthetic protocol.
2.6. Characterization
X-ray diffraction (XRD) analysis was carried out on an XRD-6000 X-ray
diffractometer (Shimadzu). Fourier transform infrared spectra (FT-IR) were recorded
on an Avatar 360 (Nicolet) instrument. Transmission electron microscopy (TEM),
scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS)
images were obtained on a Tecnai G20 (Philip) and S4800HSD (Hitachi) microscopes, respectively. Magnetic properties were measured with a LakeShore 7307
(Lakeshore Cryotronic) VSM at 300 K. Thermogravimetric analysis (TGA) was performed by a ZRY-2P thermal analyser (Shanghai Balance Instrument Company,
China). The TOC content of the aqueous solution was measured on a TOV-Vcpn
analyzer (Shimadzu).
2.7. Adsorption measurement
To investigate the adsorption dynamics of the Fe3O4@SiO2-MIP (i.e. Fe3O4@SiO2NIP, Fe3O4@SiO2, and bulk Fe3O4), 40 mg imprinted polymer was dispersed in
methanol solution of 0.1 mmol L1 BPA (20 mL). The mixture was shaken continuously at 25  C. The specimens were sampled at different time intervals: 10, 15, 20, 30,
40, 60, 80, 120, 150 and 180 min. The adsorption efciency was calculated based on
the difference of BPA concentrations before and after adsorption. To investigate the
adsorption equilibrium of the Fe3O4@SiO2-MIP (i.e. Fe3O4@SiO2-NIP, Fe3O4@SiO2,
and bulk Fe3O4), 10 mg imprinted polymer was equilibrated with varied initial
concentrations (0.02e0.5 mmol L1) of adsorbate in each tube. After 12 h, the
saturated polymer was separated by a strong magnet. The concentration of the BPA
was measured by UVevis spectrophotometer (Shimadzu UV3100) at 279 nm. In
order to estimate the selectivity of Fe3O4@SiO2-MIP for BPA, 40 mg Fe3O4@SiO2-MIP
was dispersed in 20 mL of aqueous solutions containing 0.1 mmol L1 of BPA,
bisphenol S (BPS) and phenol respectively. The mixture was shaken in HY vertical
multi-purpose vibrator at 25  C for 4 h. The concentrations of BPA, BPS and phenol
were determined by UVeVis spectrophotometer at the conditions given above. In
addition, the Fe3O4@SiO2-MIP solid with adsorbed species was regenerated with
a methanol/acetic acid (9/1, v/v) mixture. The solid was ltered off and washed with
distilled water, dried in vacuum, and reused for the subsequent adsorption of BPA.
The adsorption equilibrium of BPA on Fe3O4@SiO2-MIP was tted to Langmuir
equation:
1
1
1

Qeq
Qm bQm Ceq

(1)

Y. Li et al. / Environmental Pollution 158 (2010) 2317e2323

2319

Scheme 1. Synthesis route of surface-imprinted core-shell magnetic beads and their application for removal of BPA with the help of an applied magnetic eld.
Where Qeq (mg g1) is the equilibrium adsorbed amount of BPA, Qm (mg g1) is the
saturation capacity, Ce (mg mL1) is the equilibrium concentration, and b (mL mg1)
is the adsorption equilibrium constant.
To evaluate the adsorption kinetics of BPA, two kinetic models were used in this
case, assuming that the measured concentrations are equal to adsorbent surface
concentrations. The pseudo-rst-order rate expression of Lagergren model is
generally expressed as follows:
log Qeq  Qt

logQeq 

k1 t
2:303

(2)

Where t is the rebinding time (min), Qt (mg g1) is the adsorption capacity of
different time, Qeq (mg g1) is the equilibrium rebinding capacity, k1 (min1) is the
rst-order rate constant.
The pseudo-second-order kinetic rate equation is expressed as:
t
1
t

2
Qt
Qeq
k2 Qeq

(3)

Where k2 is the rate constant of second-order adsorption (g(mg min)1).

3. Results and discussion

3.1. Characterization of the Fe3O4@SiO2-MIP
Fig. 1 compares the XRD patterns of magnetite, Fe3O4@SiO2 and
Fe3O4@SiO2-MIP which display several relatively strong reection
peaks in the 2q region of 10e80 . The peak positions were unchanged
upon coating of SiO2 and polymerization, indicating that the crystalline structure of the magnetite was essentially maintained.
The SEM and TEM images of samples magnetite, Fe3O4@SiO2
and Fe3O4@SiO2-MIP are shown in Fig. 2. All simples displayed
spherical shape before and after being encapsulated by silica and
MIP. Fig. 2(a) shows the SEM image of the uncoated Fe3O4 microsphere. This image reveals a relatively uniform size distribution
with a mean diameter of about 330 nm. It is also seen that each
synthesized magnetite microsphere consists of a large number of
magnetite nanoparticles. Fig. 2(b) shows the SEM and TEM (inset)

images of sample Fe3O4@SiO2. It can be seen that the thickness of

the silica layer is about 18 nm, clearly showing that the magnetite
microspheres were fully coated by silica. Actually, in this process,
the thickness of the silica layer can be controlled by varying the
TEOS concentration in the reaction mixture. Fig. 2(c) clearly shows
the core-shell structure of sample Fe3O4@SiO2-MIP. The polymer
shell had a thickness of about 22 nm and appeared to be uniform
(inset), which could be attributable to the intrinsic characteristics
of the controlled/living polymerization mechanism of the RAFT
polymerization process.
Compared in Fig. 3 are the FT-IR spectra of Fe3O4, Fe3O4@SiO2,
Fe3O4@SiO2-Cl, Fe3O4@SiO2-RAFT, and Fe3O4@SiO2-MIP. As shown in
Fig. 3(a), characteristic absorption band of Fe3O4 appeared are
571 cm1. In Fig. 3(b), the peaks at 954 cm1, 799 cm1 and 1096 cm1
attributed to the stretching of SieOeH, SieO, and SieOeSi, respectively. The peaks at 678 cm1 (CeCl bond stretching vibration),
1635 cm1 (C]C bond stretching vibration), 2975 cm1 and
2928 cm1 chloromethylphenyl has been grafted onto the surface of
Fe3O4@SiO2 (Fig. 3(c)). In Fig. 3(d), the band at 1635 cm1 (C]C bond
stretching vibration) enhanced and the peak at 1054 cm1(C]S bond
stretching vibration) appeared, while the CeCl stretching band disappeared, revealing that Fe3O4@SiO2-Cl has converted to Fe3O4@SiO2RAFT. The absorption band at 1561 cm1 is strengthened distinctly,
which is the characteristic absorption of carbonyl groups of methacrylamide. At the same time, the characteristic peak of NeH bending
band at 1513 cm1 veried the successful grafting of polymer shell
from Fe3O4@SiO2 by RAFT (Fig. 3(e)).
The EDS analysis was also conducted to conrm the existence of
imprinted polymer. In Fig. 4a, the signal of oxygen and iron appeared
for Fe3O4 nanoparticles. After encapsulated with SiO2, the signal of
silica appeared, and the intensity of iron decreased owing to the
encapsulation of Fe3O4 nanoparticles by SiO2 (Fig. 4(b)). The signals
of sulfur is present for Fe3O4@SiO2-MIP, which demonstrated the
graft of imprinted polymer onto surface of Fe3O4@SiO2 (Fig. 4(c)).

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Y. Li et al. / Environmental Pollution 158 (2010) 2317e2323

Fig. 1. XRD patterns of Fe3O4 (a), Fe3O4@SiO2 (b), and Fe3O4@SiO2-MIP(c).

The TGA curves of the Fe3O4@SiO2, and Fe3O4@SiO2-MIP were

given in Fig. 5. Fig. 5(a) illustrated that in the range of 100e200  C,
the rate of weight loss for Fe3O4@SiO2 increased owing to the
dehydration in the layer of SiO2. The high rate of weight loss in the
temperature ranging from 270  C to 340  C might be due to existence of trisodium citrate. It is noted that Fe3O4@SiO2-MIP had
a rapid weight loss (Fig. 5(b)) rate between 470  C and 580  C,
which was originated from the imprinted polymer on the surface of
Fe3O4@SiO2. Hence, the results fully demonstrated the existence of
imprinted polymer.
3.2. Adsorption of BPA onto Fe3O4@SiO2-MIP
3.2.1. Magnetic properties of Fe3O4@SiO2-MIP
VSM was employed to study the magnetic properties of the
synthesized Fe3O4@SiO2-MIP. The magnetic hysteresis loop of the
sample dried at 300 K is illustrated in Fig. 6. The saturation
magnetization of Fe3O4@SiO2-MIP was reduced to 0.41 mA m2 g1
in comparison with that of the bulk Fe3O4 and Fe3O4@SiO2 (saturation magnetization are 93.49 mA m2 g1 and 10.84 mA m2 g1
respectively), but remained enough magnetic response to meet the
need of magnetic separation as can be seen from the photograph in
Fig. 6 (inset). In the absence of an external magnetic eld, a yellow
homogeneous dispersion exists. When an external magnetic eld
(0.8 T) was applied, the yellow particles were attracted to the wall
of vial in a short time (about 100 s).
3.2.2. Adsorption kinetics
Fig. 7 shows the adsorption kinetic curves of BPA over samples
Fe3O4@SiO2-MIP, Fe3O4@SiO2-NIP, Fe3O4@SiO2, and bulk Fe3O4.
Compared with Fe3O4@SiO2-NIP and bulk Fe3O4, it is evidential that

Fig. 3. FT-IR spectra of Fe3O4 (a), Fe3O4@SiO2 (b), Fe3O4@SiO2-Cl (c), Fe3O4@SiO2-RAFT
(d), and Fe3O4@SiO2-MIP (e).

a much higher adsorption capacity was achieved on Fe3O4@SiO2MIP. The removal efciency of Fe3O4@SiO2-MIP, Fe3O4@SiO2-NIP,
Fe3O4@SiO2, and bulk Fe3O4 were 81.22%, 29.73%, 5.34%, and 12.11%,
respectively. The adsorption process could be divided into two steps,
a quick step and a slow one. In the rst step, the adsorption rate was
fast, and the contact time to nearly reach equilibrium was 40 min. In
the subsequent step, the adsorption was slow to reach equilibrium.
In conclusion, higher adsorption efciency was realized in a shorter
time. The pseudo-rst-order and pseudo-second-order models
were adopted to describe the sorption kinetic data. According to
pseudo-rst-order model (eq (2)), log (QeqQt) rebinding time t
(min) resulting in a straight line with was plotted versus rebinding
time t (min) resulting in a straight line with coefcient of determination, R2, (0.9633). k1 was calculated from the slope of the linear
plot as 0.024 min1. According to pseudo-second-order model (eq
(3)), t/Qt was plotted versus coefcient of determination, R2,
(0.9976). k2 was calculated from the intercept of the linear plot as
0.012 g (mg min)1. The results show that the second-order mechanism is applicable (R2 values are the highest). These results also
suggest that the pseudo-second-order mechanism is predominant
and that chemisorption might be the rate-limiting step that controls
the adsorption process (Baydemir et al., 2007).
3.2.3. Sorption isotherm
The sorption isotherms of BPA on samples Fe3O4@SiO2-MIP,
Fe3O4@SiO2-NIP, Fe3O4@SiO2 and bulk Fe3O4 are presented in Fig. 8.

Fig. 2. The SEM and TEM images of Fe3O4 (a), Fe3O4@SiO2 (b), and Fe3O4@SiO2-MIP (c).

Y. Li et al. / Environmental Pollution 158 (2010) 2317e2323

2321

Fig. 5. TGA curves of Fe3O4@SiO2 (a), and Fe3O4@SiO2-MIP (b).

isotherm implies a homogeneous distribution of molecularly

imprinting adsorption sites on the MIP surface. It is known that
uncontrolled solution polymerization is most likely to occur,
leading to thicker and inhomogeneous polymer grafts. This can be
here minimized by using the RAFT polymerization technique.
3.2.4. Competitive adsorption, reuse, and analysis of environmental
water samples
In order to evaluate the selectivity of Fe3O4@SiO2-MIP towards
BPA, BPS and phenol were selected as potential interferents due to
their similar chemical molecular structure to that of BPA. As can be
seen from Fig. 9(a), the removal efciencies for BPA, BPS and phenol
by Fe3O4@SiO2-MIP were 71.38%, 32.34% and 23.17%, respectively,
showing that Fe3O4@SiO2-MIP had the highest molecular recognition selectivity to BPA. The adsorption selectivity over samples
(Fe3O4@SiO2-NIP, Fe3O4@SiO2 and bulk Fe3O4) is low and their
effect on the removal efciency of BPA, BPS and phenol are similar
(Fe3O4@SiO2-NIP: 22.36%, 20.18% and 18.69% respectively;
Fe3O4@SiO2: 4.86%, 4.12%, 4.97% respectively; bulk Fe3O4: 10.13%,
9.44%, and 10.46% respectively). The results indicate that the
Fe3O4@SiO2-NIP, Fe3O4@SiO2 and bulk Fe3O4 have no selectivity.

Fig. 4. EDS spectra of Fe3O4 (a), Fe3O4@SiO2 (b), and Fe3O4@SiO2-MIP (c).

By tting the experimental data with Langmuir equation, the

saturation capacity of samples Fe3O4@SiO2-MIP, Fe3O4@SiO2-NIP,
Fe3O4@SiO2 and bulk Fe3O4 for BPA were found to be 21.30 mg g1,
5.18 mg g1, 0.85 mg g1 and 1.98 mg g1, respectively. The
adsorption capacity of sample Fe3O4@SiO2-MIP is about four times
higher that of the Fe3O4@SiO2-NIP, 25 times higher than that of the
Fe3O4@SiO2, and ten times higher than that of the magnetite. The
fact that the experimental data agreed well with the Langmuir

Fig. 6. The hysteresis loop of Fe3O4@SiO2-MIP beads (Saturation magnetization is

0.41 mA m2 g1). The insert shows the separation and redispersion process of a solution of Fe3O4@SiO2-MIP in the absence (left) and presence (right) of an external
magnetic eld.

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Y. Li et al. / Environmental Pollution 158 (2010) 2317e2323

Fig. 7. Adsorption kinetic curve of Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-NIP, and Fe3O4@SiO2MIP for BPA. Other conditions: 40 mg sorbent (Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-NIP, and
Fe3O4@SiO2-MIP), 20 mL methanol solution of 0.1 mmol L1 BPA, temperature 25  C.

Fig. 9. Removal efciency of competitive molecules. Other conditions: 40 mg sorbent

(Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-NIP, and Fe3O4@SiO2-MIP), shaking time 4 h,
temperature 25  C (a). Stability and potential regeneration of the Fe3O4@SiO2-MIP(b).

Fig. 8. Adsorption isotherms of Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-NIP, and Fe3O4@SiO2MIP for BPA (a), tted Langmuir equation of Fe3O4@SiO2-MIP (b). Other conditions:
10 mg sorbent (Fe3O4, Fe3O4@SiO2, Fe3O4@SiO2-NIP, and Fe3O4@SiO2-MIP), 5 mL
methanol solution of 0.02e0.5 mmol L1 BPA, shaking time 24 h, temperature 25  C.

Fig. 10. Adsorption of Fe3O4@SiO2-MIP for BPA in real water sample. Other conditions:
40 mg sorbent Fe3O4@SiO2-MIP, 20 mL real water sample of 0.1 mmol L1 BPA,
temperature 25  C. The characterization of the real water sample: pH 6.80,
turbidity 0.35 (NTU), and TOC 2.01 mg L1.

Y. Li et al. / Environmental Pollution 158 (2010) 2317e2323

To test the stability and reusability of the Fe3O4@SiO2-MIP, ve

binding/removal (regeneration) cycles were conducted with BPA. No
obvious decrease in the adsorption capacity was observed (Fig. 9(b)),
suggesting good retention of the activity of the Fe3O4@SiO2-MIP.
In order to assess the applicability of Fe3O4@SiO2-MIP to
a practical water treatment, a drinking water sample spiked with
BPA in concentration of 0.1 mmol L1 was analyzed by the procedure mentioned above. The sampling method described in the
previous study (Liu et al., 2009,2008) was used to prepare the
working solution of BPA. As seen from Fig. 10, the results clearly
demonstrate that the Fe3O4@SiO2-MIP can produce good recovery
and can be effectively applied in the removal of BPA from environmental water samples.
4. Conclusions
This work provides a platform to prepare surface-imprinted
core-shell magnetic beads with high afnity, selectivity and easy
separation. Although the results reported here relate only to BPA,
the principles of the proposed methodology are expected to be
applicable to the removal of other EDCs from contaminated water.
We believe that these surface-imprinted core-shell magnetic beads
can be one of the most promising candidates for various applications, including environmental pollutants and biochemical separation, recognition elements in biosensors and biochips.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (50878061) and the State Key Lab of Urban
Water Resource and Environment (HIT, ESK200801).
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