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COMMUNICATION www.rsc.org/materials | Journal of Materials Chemistry

Bifunctional superparamagnetic surface molecularly imprinted polymer

core-shell nanoparticles†
Chun-Hua Lu,a Yun Wang,a Yong Li,b Huang-Hao Yang,*ab Xi Chena and Xiao-Ru Wangb
Received 27th November 2008, Accepted 13th January 2009
First published as an Advance Article on the web 26th January 2009
Published on 26 January 2009. Downloaded by University of Illinois at Chicago on 15/06/2014 23:53:02.

DOI: 10.1039/b821299f

Superparamagnetic surface molecularly imprinted polymer core- Fig. 1 illustrates the method developed for the fixation of an ATRP
shell nanoparticles were prepared via surface atom transfer radical initiator onto Fe3O4 nanoparticles, and the subsequent growth of
polymerization (ATRP) using the ATRP agent functionalized MIP layers from nanoparticles via surface initiated ATRP.‡ The
Fe3O4 support as the chain transfer agent. Fe3O4 nanoparticles were first coated with a thin silica layer through
a sol-gel approach to obtain silica-Fe3O4 composites (designated
Fe3O4@SiO2). Analysis by transmission electron microscopy reveals
Molecularly imprinted polymers (MIPs) are artificial, template-made that the Fe3O4 nanoparticles have a mean diameter of about 300 nm
receptors with the ability to recognize and to specially bind the target (Fig. 2a). After coating with a silica layer, core-shell Fe3O4@SiO2
molecule.1 The stability, ease of preparation and low cost of these nanoparticles with a thin silica layer of about 10 nm were obtained
materials have led to their assessment as substitutes for antibodies or (Fig. 2b and d). Actually, in this process, the thickness of the silica
enzymes in chemical sensors, catalysis and separations. Presently shell can be controlled by varying the proportion of TEOS in the
techniques used to prepare MIPs most often result in material reaction mixture. The outer silica shell functions as a protective layer
exhibiting high selectivity but poor site accessibility to the target
molecule. To advance MIPs to real application, new molecular
imprinting morphologies and manufacturing techniques need to be
developed. Recently, thin MIP layers2 and MIP nanoparticles3 have
attracted more and more attention because they have the potential to
overcome mass transfer limitations and nonquantitative recovery
of the template molecule seen for MIPs fabricated by conventional
bulk polymerization.
However, to the best of our knowledge, there is still not a simple
and general method to prepare thin MIP layers on functional
nanoparticles (magnetic nanoparticles, quantum dots or gold nano-
particles) for hybrid nanomaterials. Functional nanoparticles are
being developed for host of biomedical and biotechnological appli-
cations. For example, commercially available magnetically nano-
particles are used for drug delivery and rapid biological separations,4
quantum dots have been used for fluorescence assays in cells,5 and
colloidal gold nanoparticles have been used for biosensors and gene
therapy.6 Combination of MIPs and functional nanoparticles will
doubtless broaden the use of MIPs.
In this communication, we present a method for making well
defined bifunctional (molecularly imprinted and magnetically sepa-
rable) Fe3O4/MIP core/shell nanoparticles by atom transfer radical
polymerization (ATRP). ATRP is a new class of controlled living
radical polymerization.7 It has been a popular means to graft polymer
layers,8 including MIP layers,2c,d from solid supports because of its
good control over the product molecular weight and dispersity.

a
The Key Lab of Analysis and Detection Technology for Food Safety of the
MOE, College of Chemistry and Chemical Engineering, Fuzhou University,
Fuzhou, P.R. China. E-mail: hhyang@fio.org.cn; Fax: +86 532 88963259;
Tel: +86 532 88963259
b
The First Institute of Oceanography, SOA, Qingdao, P.R. China
† Electronic supplementary information (ESI) available: Fig. S1 The
absorption spectrum of bisphenol A, Fig. S2 The absorption spectrum Fig. 1 Outline of the fixation of an ATRP agent onto Fe3O4@SiO2
of 4,40 -biphenol, Fig. S3 The absorption spectrum of b-estradiol. See nanoparticles and the grafting of MIP shell from Fe3O4@SiO2 nano-
DOI: 10.1039/b821299f particles via ATRP.

This journal is ª The Royal Society of Chemistry 2009 J. Mater. Chem., 2009, 19, 1077–1079 | 1077
Published on 26 January 2009. Downloaded by University of Illinois at Chicago on 15/06/2014 23:53:02.
Fig. 2 TEM images of (a) Fe3O4 nanoparticles, (b, d) Fe3O4@SiO2
nanoparticles, and (c, e) Fe3O4@MIP nanoparticles.
for the inner Fe3O4 core. It also alters the surface chemistry of Fe3O4
to enable postsynthetic modification of the surfactant chemistry.
Previous research has shown that dense polymer shells with
tunable thickness can be easily grafted from the surfaces of solids or
nanoparticles with controlled behavior via surface initiated ATRP.8
The resulting superparamagnetic surface-imprinted nanoparticles
(designated Fe3O4@MIP)x were characterized by transmission
electron microscopy (TEM). From the TEM images (Fig. 2c and e),
a polymer shell with well defined shape and configuration was readily
observed on the Fe3O4@SiO2 nanoparticles surface with light
contrast. The polymer shell had an average thickness of about 15 nm
and appeared to be uniform.
The magnetic properties of the nanoparticles were studied by
a SQUID magnetometer. Magnetic measurement indicates that
Fe3O4@MIP nanoparticles have superparamagnetism properties and
large saturation magnetization (70.4 emu/g). These properties allow
for the complete separation of these nanoparticles in a short time
(about 1 min) by a strong magnet (Fig. 3).
The template, functional monomer and cross-linking agent used in
this study are bisphenol A, 4-vinlpyridine (4-VP) and ethylene glycol
dimethacrylate (EGDMA), respectively. The binding properties of
Fe3O4@MIP nanoparticles towards bisphenol A were determined by
measuring the uptake of bisphenol A in acetonitrile over a range of
Fig. 3 Pictures of a solution of Fe3O4@MIP with and without a magnet.
1078 | J. Mater. Chem., 2009, 19, 1077–1079
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Fig. 4 Amount of bound bisphenol A by (A) Fe3O4@MIP and (D)
Fe3O4@NIP; amount of bound 4,40 -biphenol by (B) Fe3O4@MIP and
(E) Fe3O4@NIP; amount of bound b-estradiol by (C) Fe3O4@MIP and
(F) Fe3O4@NIP.
concentration from 0.02 to 0.3 mmol/L. In the binding analysis, 5 mg
Fe3O4@MIP nanoparticles were suspended in bisphenol A solutions
at difference concentrations. The samples were incubated on a rock-
ing table for 1 h at room temperature. After separation with
a magnet, the supernatant was withdrawn and analyzed with UV
absorption to quantify the amount of bisphenol A adsorbed by
Fe3O4@MIP nanoparticles. The results showed that the Fe3O4@-
MIP nanoparticles have much higher capacity than those of the
control Fe3O4@NIP nanoparticles (Fig. 4). To further evaluate the
specificity of the Fe3O4@MIP nanoparticles, the binding of several
structurally related compounds to Fe3O4@MIP nanoparticles was
studied and compared (Fig. 4). All the compounds being evaluated
exhibited lower binding capability to the Fe3O4@MIP nanoparticles
than those of the original template.
To gain further insight into the phenomenon of bisphenol A
binding by the Fe3O4@MIP nanoparticles, the binding data were
fitted into a Langmuir isotherm model. In the Langmuir model,
the binding constant (1/Kd) and saturation capacity (Bmax ¼ B +
Bunbound) can be estimated graphically from a linearized version of the
model by plotting the adsorption isotherm in a Scatchard format, B/F
¼ (Bmax
B)/Kd. Curve-fitting gave a dissociation constant of
22.27 mmol/L with a saturation capacity of 23.29 mmol/g.
Binding kinetics of the template bisphenol A with Fe3O4@MIP
nanoparticles were evaluated. The Fe3O4@MIP nanoparticles
require only 60 min to reach equilibrium. MIP particles prepared by
the conventional bulk technique require about 300 min to reach
equilibrium. These data prove that a thin layer of MIP could make
the imprinted sites more accessible.
Based on the results above, which confirm the imprinting
effect generated by the template bisphenol A in the Fe3O4@MIP
nanoparticles, we further investigated the potential use of these
nanoparticles as adsorbents for the selective extraction of bisphenol A
from spiked water samples. Tap water was spiked with bisphenol
A at three concentration levels: 0.5, 1.0 and 2.5 mmol/L. 15mg of the
Fe3O4@MIP nanoparticles were suspended in 10 mL of bisphenol A
solution, and the mixture was incubated for 1 h at room temperature.
Then the nanoparticles were separated by a magnet. The supernatant
This journal is ª The Royal Society of Chemistry 2009

Table 1 Analytical parameters of the proposed methoda
Bisphenol A in water Detected concentration Recovery RSD
samples (10
6 mol/L) (10
6 mol/L) (%) (%)
0.5 0.52 104.0 6.4
1.0 1.05 105.0 3.5
2.5 2.41 96.4 4.3
a
n ¼ 6.
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was discarded. The nanoparticles were washed with methanol twice.
Finally, the preconcentrated bisphenol A was eluted from the isolated
nanoparticles with 0.5 mL methanol (containing 10% acetic acid).
The eluent was injected into the HPLC system for analysis. Table 1
lists the recoveries and concentrations found for the target bisphenol
A, expressed as the mean value (n ¼ 6). Recoveries of bisphenol A
ranged between 96.4% to 105.0% for all three samples and the relative
standard deviation of recoveries ranged from 3.5% to 6.4%, which
demonstrated the good precision of the proposed method.
In summary, we have developed a method for preparation of
superparamagnetic surface MIP core-shell nanoparticles. The
controllable nature of ATRP allows the growth of uniform MIP layer
with adjustable thickness. The Fe3O4@MIP nanoparticles can be
directly used in magnetic separating sorbent assays. Moreover, the
Fe3O4@MIP are within the biological size restrictions and may have
potential used in controlled drug delivery, as biochemical sensors
and for trace enrichment of specific targets in vivo. Finally, due to the
versatility of the ATRP route, the method developed here can be
potentially used to prepare MIP layers on other functional nano-
particle (such as quantum dots, gold nanoparticles and carbon
nanotubes) surfaces for new hybrid materials. Work in this direction
is already in progress and will be communicated in due course.
This work was jointly supported by the National Natural
Science Foundation of China (No. 20775019, No. 20735002), the
Hi-Tech Research and Development Program of China (No.
2006AA09Z168), the Natural Science Foundation of Shandong
province (No, Y2006B01) and Young Scientist Foundation of SOA
(2007601).
Notes and references
‡ Details for the fixation of ATRP initiator onto Fe3O4 nanoparticles are
as follows. Fe3O4 nanoparticles and Fe3O4@SiO2 nanoparticles were
prepared according to ref. 9. Dried Fe3O4@SiO2 (300 mg), 3-amino-
propyltrimethoxysilane (500 mL) and 20 mL absolutely dry toluene were
mixed in a conical flask under nitrogen atmosphere. With mechanical
stirring, the mixture was allowed to react at a constant temperature of
90  C for 48 h, and the nanoparticles produced were separated from the
mixture by a magnet. The product was washed with toluene 5 times
and then washed with methanol 5 times. Finally, the obtained
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Fe3O4@SiO2@NH2 was dried under vacuum at room temperature.
Fe3O4@SiO2@NH2 (300 mg), dichloromethane (26 mL), triethylamine
(500 mL), and a catalytic amount of DMAP were added individually into
a conical flask. Then 2-bromoisobutyrylbromide (400 mL) was added, and
the mixture was kept first at 0  C for 2 hours and then at room
temperature for 12 hours. The product was separated from the mixture by
a magnet. For purification, the Fe3O4@SiO2@Br was washed with
dichloromethane 5 times. Finally, the Fe3O4@SiO2@Br were dried under
vacuum at room temperature.
x Details for the preparation of Fe3O4@MIP nanoparticles are as
follows. The preparation of Fe3O4@MIP nanoparticles was performed in
a conical flask containing 150 mg of Fe3O4@SiO2@Br suspended in
a polymerization mixture consisting of CuBr (0.1 mmol), 1,10 ,4,7,70 -
pentamethyldiethylenetriamine (0.15 mmol), the functional monomer 4-
VP (6 mmol), the cross-linking monomer EGDMA (30 mmol), and
template bisphenol A (1 mmol) dissolved in 15 mL acetonitrile. After
sealing, mixing, and purging the mixture with nitrogen, the flask was
placed in a thermostatted oil bath at 70  C with mechanical stirring for 24
h. The reaction product was then separated from the polymerization
mixture by a magnet. The control Fe3O4@NIP nanoparticles was
prepared and washed using the same recipe but without the addition of
the template bisphenol A.
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