Colloids and Surfaces A: Physicochem. Eng.

Aspects 415 (2012) 6876

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Colloids and Surfaces A: Physicochemical and
Engineering Aspects
j our nal homepage: www. el sevi er . com/ l ocat e/ col sur f a
Fabrication and characterization of temperature-, pH- and
magnetic-eld-sensitive organic/inorganic hybrid poly (ethylene glycol)-based
hydrogels
Yang Wang, Aijuan Dong, Zhicheng Yuan, Dajun Chen

State Key Laboratory for Modication of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Shanghai 201620, Peoples Republic of China
h i g h l i g h t s
A new kind of magnetic nanoparti-
cle was prepared via co-precipitation
technique.
Novel multiple stimulus-responsive
hydrogels were prepared by in situ
polymerization.
The mf-NC hydrogels have
T/pH/magnetic sensitivity and
good mechanical properties.
The mf-NC hydrogel can continue
swelling under an alternating mag-
netic eld.
g r a p h i c a l a b s t r a c t
a r t i c l e i n f o
Article history:
Received 6 July 2012
Received in revised form
21 September 2012
Accepted 1 October 2012
Available online 9 October 2012
Keywords:
Magnetic-sensitive
Thermo-sensitive
pH-sensitive
Magnetic ATFe
3
O
4
nanoparticles
P(MEO
2
MA-co-OEGMA-co-AAc) hydrogel
a b s t r a c t
In this paper, we successfully fabricated a new kind of multiple stimulus-responsive organic/inorganic
hybrid hydrogels by combining dual stimuli-responsive poly (2-(2-methoxyethoxy) ethyl
methacrylate-co-oligo (ethylene glycol) methacrylate-co-acrylic acid) (PMOA) hydrogel with mag-
netic attapulgite/Fe
3
O
4
(ATFe
3
O
4
) nanoparticles. First, the magnetic nanoparticle was prepared via
co-precipitation technique in aqueous suspension of puried attapulgite. The obtained ATFe
3
O
4
nanoparticles were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, eld
emission scanning electron microscopy and vibrating sample magnetometer. Compared with pure
attapulgite, the ATFe
3
O
4
exhibited better superparamagnetic properties. Then, the ATFe
3
O
4
was
introduced into the dual-responsive (temperature and pH) PMOA hydrogel network by in situ poly-
merization. The morphology, responsive behaviors and tensile properties of the prepared hydrogels
were systematically characterized by eld emission scanning electron microscopy, vibrating sample
magnetometer, swelling/re-swelling behaviors and tensile testing. The results showed that the ATFe
3
O
4
nanoparticles were well dispersed in the hydrogel matrix, and the multi-functional ATFe
3
O
4
/PMOA
nanocomposite hydrogels had not only temperature/pH sensitivity and good mechanical properties, but
also magnetic functionality. The tunable superparamagnetic behavior of these hydrogels depended on
the amount of ATFe
3
O
4
. In addition, the multi-functional ATFe
3
O
4
/PMOA nanocomposite hydrogels
can continue to swell under an alternating magnetic eld after equilibrium swelling in deionized water.
2012 Elsevier B.V. All rights reserved.

Corresponding author. Tel.: +86 21 67792891; fax: +86 21 67792855.

E-mail address: cdj@dhu.edu.cn (D. Chen).
1. Introduction
Smart hydrogels are three-dimensional network structure that
change their physical and (or) chemical properties in response to
external environmental stimuli [13], such as temperature, pH,
pressure, electric eld, magnetic eldandlight andsoon. Due tothe
0927-7757/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2012.10.009
Y. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 415 (2012) 6876 69
unique stimulusresponse property, smart hydrogels are widely
applied in drug controlled release, biosensors, chemical convert-
ers, articial muscles, tissue engineering, and molecular separation
system and so on [47]. Currently, the smart hydrogels can be
mainly divided into single-sensitive hydrogels [815] (tempera-
ture (T), pH, electric eld, magnetic eld and light), dual-sensitive
hydrogels [1620] (TpH sensitive, pH salt sensitive and mag-
netic thermal sensitive), multiple-sensitive hydrogels [17,2123]
(TpHmagnetic response, TpHlight response).
In the past few decades, single and dual-sensitive hydrogels
have attracted considerable attention. However, fromthe develop-
ment of practical applications, the fabrication of multiple-sensitive
hydrogels would be much more attractive if they could respond
to at least three stimulation, such as possessing T-, pH- and
magnetic/electric/light-sensitive simultaneously. Such multiple-
responsive materials are of interest for a variety of applications
rangingfrommagnetic/electric/light separationor drugreleasesys-
tems to sensors and actuators.
Presently, the incorporation of magnetic nanoparticles (Fe
3
O
4
,
-Fe
2
O
3
or CoFe
2
O
4
) into T-/pH-sensitive microgels/hydrogels
matrix to form triple-response hydrogels can be easily achieved
and has received increasing interest. For example, Lang and
co-workers [24] prepared polysaccharide-based hydrogels with
pH- and thermo-sensitive property by the copolymerization of
maleilated carboxymethyl chitosan with N-isopropylacrylamide,
and then fabricated their magnetic hybrid hydrogels by in situ
deposition of magnetic iron oxide nanoparticles into the porous
hydrogel networks. Bhattacharya et al. [21] described the syn-
thesis and characterization of multifunctional hybrid microgels
that exhibit temperature, pH and magnetic triple stimuli-response
by in situ formation of iron oxide nanoparticles in the microgel
structure. However, in situ formation of magnetic nanoparticles
in polymer network needed to be treated with alkaline solution.
In this case the polymer gels network would be easily destroyed,
which decreased the overall performance of the gels. In order to
overcome this shortcoming, some researchers began to use ready-
made magnetic particles introduced directly into the polymer gels
to achieve the magnetic response of polymer gels.
However, it is well-known that poor mechanical properties of
hydrogels severely restrict their practical applications. Currently,
incorporating clay into hydrogel matrix has been proved to be
an effective and simple method to enhance the mechanical prop-
erties of hydrogels [2531]. Attapulgite (AT) is a type of natural
brillar aluminum silicate with abundant hydroxyl groups on the
surfaces [31]. Decorating AT with Fe
3
O
4
magnetic nanoparticles
(ATFe
3
O
4
) may give birth to novel chemical and physical prop-
erties, expecting to be applied in polymeric gels system. To date,
the hybrid materials on the combination of magnetic nanoparti-
cles (such as Fe
3
O
4
) with responsive hydrogels have been reported
[14,19,3234]. Echeverria and co-worker [14] have reported that
UCST-like hybrid poly (acrylamide-acrylic acid)/Fe
3
O
4
microgels
by the incorporation of metal oxide nanoparticles into microgels.
They investigated the effect of Fe
3
O
4
nanoparticles on morphol-
ogy, thermo-sensitivity and elasticity. Recently, Chanana et al. [34]
have prepared nanocomposites based on magnetite and thermore-
sponsive poly (2-(2-methoxyethoxy) ethyl methacrylate)-co-oligo
(ethyleneglycol) methacrylate) (P(MEO
2
MA-co-OEGMA)) copoly-
mers. The advantage of these polymers is that the lower critical
solution temperature (LCST) in water can be easily adjusted by
the oligo (ethylene glycol) chain length in a wide temperature
range from 24 to 95

C. A similar study was report by Gelbrich

[19] in the preparation of magnetic coreshell nanoparticles that
were composed of nanosized superparamagnetic iron oxide cores
and a copolymer shell. The shell which consists of OEGMA and
methoxyethyl methacrylate (MEMA) copolymers shows a LCST in
water.
In our previous publication [31,35], it was demonstrated that
composition of MEO
2
MA, OEGMA and acrylic acid (AAc) gels
(PMOA) can be tailored to get temperature and pH response, and
the mechanical properties of the gel can be signicantly improved
by adding the AT nanoparticles. Here, the aimof the present study
was the preparation of hydrogels with excellent mechanical prop-
erties that are sensitive to temperature, pH and magnetic eld.
Therefore, we fabricated a new kind of smart organic/inorganic
hybrid hydrogel by combining dual stimuli-responsive PMOA
hydrogel with magnetic ATFe
3
O
4
nanoparticles. First, the mag-
netic nanoparticle, attapulgite/Fe
3
O
4
(ATFe
3
O
4
), was preparedvia
a simple co-precipitation method. Then, the ATFe
3
O
4
was suc-
cessfully introduced into the dual-responsive (T and pH) PMOA
network by in situ polymerization. The microstructures and vari-
ous properties of the ATFe
3
O
4
and the prepared hydrogels were
systematically characterized by Fourier transform infrared spec-
troscopy (FT-IR), X-ray diffraction (XRD), eld emission scanning
electron microscopy (FESEM), vibrating sample magnetometer
(VSM), swelling/re-swelling behaviors and tensile testing.
2. Experimental
2.1. Materials
2-(2-Methoxyethoxy) ethyl methacrylate (MEO
2
MA, 97%) was
purchased from TCI Chemical Co. Tokyo, Japan. Oligo (ethylene
glycol) methyl ether methactylate (OEGMA, average Mn =475, the
number of EO units 89) was purchased from SigmaAldrich Co.
Attapulgite (AT) was obtained from Xuyi Colloidal Co. Jiangsu,
China. Acrylic acid (AAc), iron dichloride (FeCl
2
), iron chloride
(FeCl
3
), sodiumhydroxide (NaOH), potassiumpersulfate (K
2
S
2
O
8
),
and sodium hydrogen sulte (NaHSO
3
) were purchased from
SinopharmChemical Reagent Co. Ltd. All these reagents were used
as received.
2.2. Preparation of the magnetic attapulgite (ATFe
3
O
4
) particles
The crude AT powder contains a lot of impurities and dirt.
First, AT was puried before the preparation of magnetic particles,
according to our previous work [36]. Puried AT (2.4g) and deion-
izedwater (320ml) were addedto a ask andthe pHof the aqueous
dispersion was adjusted to 8. Then 0.4MFeCl
3
solution (20ml) was
added into the ask, dispersed in an ultrasonic bath (50kHz) for
30min. 0.9MFeCl
2
solution (20ml) was added to the aqueous dis-
persion. The mixture was treated in the ultrasonic bath for 15min
andthen1MNaOHsolutionwas droppedinto the ask until the pH
value of the aqueous dispersion reached 10 and the black precip-
itate appeared immediately. Then, the mixture was treated in the
ultrasonic bath for another 1.5h. After that, the product was cen-
trifuged at 12000rpmfor 5min and washed with deionized water
several times to remove unreacted ions, and dried in a vacuum
oven at 70

C for 24h. The weight fraction of Fe

3
O
4
in ATFe
3
O
4
composite is nearly 30wt%.
2.3. Preparation of the multi-functional ATFe
3
O
4
/PMOA
nanocomposite hydrogels
Referring to our previous work [31], the multi-functional
ATFe
3
O
4
/PMOA nanocomposite hydrogels (mf-NC hydrogels)
were prepared by in situ free radical polymerization in ethanol
solution. First, ATFe
3
O
4
with certain weight was dispersed in
the ethanol solution under ultrasonic vibration for 1.5h. Then,
the monomers of MEO
2
MA, OEGMA and AAc were added into the
ATFe
3
O
4
solutionandwere allowedto mix under ultrasonic vibra-
tion for 30min. To initiate the polymerization, a certain amount
of redox initiators which were composed of K
2
S
2
O
8
and NaHSO
3
70 Y. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 415 (2012) 6876
Table 1
Composition of mf-NC hydrogels.
Samples ATFe
3
O
4
(wt%) POMA (wt%) Ethanol (wt%)
Pure PMOA 0 57 43
mf-NC
1
1 56 43
mf-NC
2
3 55 42
mf-NC
3
5 54 41
Note: 1wt% K
2
S
2
O
8
and NaHSO
3
as initiators =2ml.
were added into the mixture with stirring for 10min. Finally, the
mixture was put into a vacuum oven for 5min to remove any
air bubbles. The composite solution was injected into glass tubes
(diameter =5mm, length=120mm) at room temperature under
vacuum for 24h. When the reaction is completed, the pieces of
glass tubing lled with NC gels were carefully broken, and the gel
columns were immersed in deionized water for at least 3 days to
remove the unreacted reactants. During this period the water was
replaced several times. For comparison, the pure PMOA hydrogel
was also prepared with the same method. The different composi-
tion of the samples is listed in Table 1. The sample codes mf-NC
1
,
mf-NC
2
and mf-NC
3
corresponded to the ATFe
3
O
4
contents of 1,
3 and 5wt%, respectively.
2.4. Characterizations
2.4.1. Fourier transforminfrared spectroscopy (FT-IR)
The dried AT, Fe
3
O
4
and ATFe
3
O
4
samples were tested by a
Nicolet Impact NEXUS-8700 FT-IR in the range of 4004000cm
1
.
The dried sample was ground with dried potassiumbromide (KBr)
powder and compressed into a disc, and then was subjected to
analysis.
2.4.2. X-ray diffraction (XRD)
The X-ray diffraction of samples was performed on a Rigaku
(Japan) DMAX-2550X-ray diffractometer. The CuKradiationwith
a wavelength of =1.54178

A was used.
2.4.3. Field emission scanning electron microscopy (FESEM)
FESEM(Hitachi S-4800) was used to observe the morphology of
powdered AT and ATFe
3
O
4
, and the distribution of mf-NC hydro-
gels. The powdered samples were dispersed in aqueous solution
(15%) under the ultrasonic vibration for 10min, then the mixture
solution was dropped to a clean coverslip in order to observe the
morphology when it is dried. The fully swollen mf-NC hydrogels
were dried at room temperature for several days until all water
volatilized. The cross-sections and the vertical sections of the dried
mf-NC hydrogels were coated with gold and measured by FESEM.
2.4.4. Vibrating sample magnetometer (VSM)
The magnetization measurements of ATFe
3
O
4
, Fe
3
O
4
and mf-
NC hydrogels were carried out at room temperature using a
vibrating sample magnetometry (PPMS VSM, Model6000) with a
maximumapplied eld of 1T.
2.4.5. Measurements of re-swelling behaviors in an alternating
magnetic eld
The re-swelling kinetics of hydrogels was measured gravimet-
rically in a home-made alternating magnetic eld (AMF) (as shown
in Fig. 1) at room temperature. The AMF was generated by rotat-
ing the sample to cut magnetic induction lines. The rotating speed
was 60rpm. The mf-NC
3
hydrogels was allowed to swell to the
equilibrium in deionized water at room temperature before the
re-swelling measurement. Then, the full swollen hydrogels were
transferred into the AMF. At regular time intervals, the swollen
samples were removed fromthe magnetic eld and weighted after
Fig. 1. Schematic illustration of the re-swelling measurement of the mf-NC
3
hydro-
gels in the AMF.
blotting off the excess water from the sample with a lter paper.
The re-swelling ratio is calculated as follows:
Re-swelling ratio =
W
t
W
s
W
s
100% (1)
where W
s
is the weight of the swollen equilibrium hydrogel and
W
t
is the weights of re-swelling hydrogel at a given time, respec-
tively. For comparison, the re-swelling process of mf-NC
3
hydrogel
without the AMF was also measured and recorded.
2.4.6. Testing of thermo- and pH-responsive behaviors
In order to conrmthe thermo- and pH-responsive behaviors of
the mf-NC hydrogels, the swelling ratios of the mf-NC hydrogels in
deionized water and different pH buffer solutions were measured
with the same method, as reported in the literature [37]. The effect
of temperature on the equilibrium swelling ratio was measured
at the temperature ranging from 25

C to 55

C. At each temper-
ature, hydrogels need 12h to expel water and to achieve the new
equilibrium. BrittonRobinson buffer solutions with the same ionic
strength and different pH values (1.98, 3.29, 4.56, 5.72, 6.8, 7.96,
9.15 and 10.38) were measured by pH meter. The pH-responsive
behavior of mf-NC hydrogels was assessed at room temperature
(25

C) by immersing hydrogels in different pH buffer solutions

for 130h. The swollen samples were removed from solution and
weighted after blotting off the excess water fromthe sample with
lter paper. The equilibrium swelling ratio (ESR) is calculated as
follows:
ESR =
W
t
W
d
W
d
(2)
where W
t
is the weight of the swollenhydrogel at giventime during
swelling and W
d
is the weight of dry hydrogel.
2.4.7. Tensile mechanical properties
The prepared hydrogels were fully swollen in deionized water
for some days before subjecting to tensile tests using a Dejie DXLL-
2000 at 25

C, as reported in our previous publication [31]. All

samples have the same size (6mmdiameter 60mmlength). The
conditions of tensile measurement are as follows: sample length
between jaws was 40mm, and crosshead speed was 10mmmin
1
.
At least 5 samples were tested for each type of hydrogels and the
data were averaged.
Y. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 415 (2012) 6876 71
Fig. 2. FT-IR of the ATFe
3
O
4
(a), Fe
3
O
4
(b) and puried AT (c).
3. Results and discussion
3.1. Properties of the magnetic attapulgite (ATFe
3
O
4
)
nanoparticle
3.1.1. FT-IR analysis
The FT-IR spectra of sample ATFe
3
O
4
, Fe
3
O
4
and puried AT
are shown in Fig. 2a, b and c, respectively. As can be seen from
Fig. 2, a broad band exists at around 3400cm
1
, assignable to the
characteristic peak of OH groups, resulting from the absorbed
water or hydroxyl on the surface of AT and Fe
3
O
4
. In the spectrum
of Fig. 2c, the absorbance bands at 1033.3cm
1
, 986.9cm
1
and
475.8cm
1
can be ascribed to the characteristic peaks of AT. The
peaks at 565.1cm
1
in Fig. 2b can be assigned to the vibrations
Fe O of Fe
3
O
4
particles [38]. It is found that the absorption bands
of ATFe
3
O
4
composite at 1030.8cm
1
, 987.7cm
1
and513.6cm
1
alsoappearedinFig. 2a, whichreveals theexistenceof ATandFe
3
O
4
in the composite.
3.1.2. XRD analysis
In order to understand the structure of the synthesized compos-
ite ATFe
3
O
4
, powder XRD has been recorded in Fig. 3. According
to Ref. [39], the peaks of composite at 2 =30.3

, 35.5

, 43.1

,
57.0

and 62.7

can be assigned to Fe
3
O
4
. The peaks of ATFe
3
O
4
at 2 =8.2

, 13.8

, 19.7

and 27.5

are consistent with the primary

diffraction of (110), (200), (040) and (400) planes of AT [40,41],
Fig. 3. X-ray diffraction pattern for the puried AT, Fe
3
O
4
and ATFe
3
O
4
.
respectively, indicating that the structure of AT was not destroyed
during the decorating process. However, it should be noted that the
peak intensity of AT decrease after decorating. It can be concluded
that the surface of AT was covered by Fe
3
O
4
.
3.1.3. Morphology and structure of ATFe
3
O
4
nanoparticle
Fig. 4(a) shows the FESEM images of the puried AT. It is clear
that AT exhibits a brous structure. The size of a single ber can be
clearly observed, which was about 50nm in width and 0.51m
in length. The morphology of the obtained composite is displayed
in Fig. 4(b). Combined with the result of FT-IR, it is evident that the
surface of AT is decorated with Fe
3
O
4
nanoparticles. And the Fe
3
O
4
nanoparticles are in the range of 1030nm in diameter and the
larger particles are aggregates of two or more small Fe
3
O
4
particles.
3.1.4. Magnetic properties of ATFe
3
O
4
particle
The magnetic hysteresis loops of the puried AT, Fe
3
O
4
,
ATFe
3
O
4
nanoparticles were measured at 300K are shown in
Fig. 5. The specic saturation magnetization (
s
) of as-prepared
AT, ATFe
3
O
4
, and Fe
3
O
4
is 0, 52.63 and 63.67emu/g, respectively.
It demonstrates that the ATFe
3
O
4
composite has a typical super-
paramagnetic characteristic, which can be mainly attributed to the
small particle size of Fe
3
O
4
nanoparticles.
Fig. 4. FESEMimages of puried AT (a) and ATFe
3
O
4
(b) nanoparticles.
72 Y. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 415 (2012) 6876
Fig. 5. Magnetic hysteresis loops for puriedAT, Fe
3
O
4
andATFe
3
O
4
nanoparticles.
3.2. Characterization of the multi-functional ATFe
3
O
4
/PMOA NC
hydrogels
3.2.1. The structure and morphology of the mf-NC hydrogels
Fig. 6 shows the morphology of the pure PMOA and mf-NC
hydrogels. By comparing with morphology of the pure hydrogel
(Fig. 6(a) and (b)), it is clear that the rod-like ATFe
3
O
4
particles
are successfully introduced into the hydrogel matrix (Fig. 6(cf)
indicated by red circle). Compared with mf-NC
3
(Fig. 6(e) and
(f)), mf-NC
1
presents a relatively uniform dispersion. That can be
explainedby the fact that the ATFe
3
O
4
content of mf-NC
3
is higher
thanthat of mf-NC
1
, leading toa slight agglomeration. Additionally,
it should be mentioned that the structure and morphology of the
rod-like magnetic nanoparticles were not damaged and consistent
Fig. 7. The vertical sections of mf-NC
3
withthe applicationof a static magnetic eld.
with the morphology as shown in Fig. 4. Therefore, due to the pres-
ence of magnetic ATFe
3
O
4
nanoparticles, the prepared hydrogels
are expecting to fulll magnetic functionalization, which can be
used in controlled release of drugs under magnetic eld.
3.2.2. Magnetic properties of the mf-NC hydrogels
The fully swollen mf-NC
3
was dried at room temperature on a
magnet for several days until all water volatilized. Then the ver-
tical section of the dried sample was measured by FESEM. Fig. 7
shows FESEMimage of the vertical sections of mf-NC
3
under a static
magnetic eld. Compared with the same sample without the mag-
netic eld (Fig. 6(f)), the arrangement of the magnetic ATFe
3
O
4
nanoparticles is more perpendicular to the surface of the hydro-
gel matrix (as shown inside red circle). In other words, ATFe
3
O
4
nanoparticles were arranged along the direction of the magnetic
eld fromdisorder to order due to the application of the magnetic
eld, which is similar to the orientation of the polymer to a certain
Fig. 6. FESEMimages of pure PMOA and dried mf-NC hydrogel with ATFe
3
O
4
content of 1% and 5%. ((a), (c), (e) and (b), (d), (f) corresponding to the cross sections and the
vertical sections of pure PMOA, mf-NC
1
and mf-NC
3
, respectively). The magnication times of (a) and (bf) are 5000 and 20000, respectively.
Y. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 415 (2012) 6876 73
extent. In addition, it also can be seen fromthe Fig. 7 that a part of
ATFe
3
O
4
nanoparticles are agglomeratedobviously withresponse
to the magnetic eld. These results suggest that under the exter-
nal magnetic eld, the internal morphology of the hydrogel can be
changed due to the presence of the magnetic nanoparticles. Thus,
froma macroscopical point of view, the hydrogel is endowed with
magnetic response property.
Additionally, we built a simple magnetically responsive device
using a magnet for testing the apparent magnetic response, as
shown in Fig. 8(I(a)). The apparent magnetic response results of
pure PMOA and mf-NC hydrogels are shown in Fig. 8(I(be)). It
can be seen from Fig. 8(I(b)) that when the pure PMOA hydrogel
is close to the magnet innitely, there is no magnetic response.
That can be proved that the pure PMOA hydrogel itself as a
matrix material has no magnetic response. However, it obviously
can be seen from Fig. 8(I(ce)) that all mf-NC hydrogels have a
magnetic response because of the introduction of the magnetic
ATFe
3
O
4
. When the mf-NC hydrogels are getting close to the
magnet, they will be attracted towards the magnet. According to
the scale of Fig. 8(I), the relationship between the sensing dis-
tance (SD) and the content of ATFe
3
O
4
is shown in Fig. 8(II).
It can be seen that linear relation with a regressive coefcient
of 0.983 is obtained. The values of SD are 0cm for pure PMOA,
nearly 0.1cm for mf-NC
1
, 0.3cm for mf-NC
2
and 0.6cm for mf-
NC
3
, respectively. It is quantitatively understood that the magnetic
responsiveintensityof themf-NChydrogels increases withincreas-
ing of ATFe
3
O
4
nanoparticles content. This result is also supported
by magnetizationmeasurements. The magnetization(M) of various
mf-NChydrogels was measuredby a vibrating sample magnetome-
ter, as shown in Fig. 8(III). The magnetic measurement studies
show that all the mf-NC hydrogels exhibited superparamagnetic
behavior, demonstrated by the symmetrical sigmoid shape of the
magnetization curves exhibiting no hysteresis. The magnetiza-
tion values of mf-NC
1
, mf-NC
2
and mf-NC
3
are 0.28, 0.85 and
1.30emu/g, respectively. It is clear that by increasing the ATFe
3
O
4
concentration, the saturation magnetization increases as the den-
sity of magnetic nanoparticles increases. Similar results were
reportedby Liuet al. onthe PVA/Fe
3
O
4
nanocomposite system[42].
Fig. 9 shows the re-swelling behavior of the mf-NC
3
hydrogel in
an alternating magnetic eld (AMF). It can be seen from Fig. 9(a)
that the mf-NC
3
hydrogel can further swell in the AMF after equi-
librium swelling in deionized water. However, when the mf-NC
3
hydrogel is rotated without the AMF, it is almost never re-swelling.
The photos of comparison samples are shown in Fig. 9(b). This dif-
ference can be interpreted that by rotating the sample between
the two magnets, the magnetic induction lines were cut repeat-
edly, and then an alternating magnetic eld is generated. Although
the hydrogel has reached equilibriumswelling in deionized water,
the distribution of the magnetic ATFe
3
O
4
nanoparticles in the mf-
NC
3
hydrogel is still very close. This can be explained by the fact
that these single-domain magnetic nanoparticles being adhesively
attached to the polymer chains, they have no translational diffu-
sion without the application of the AMF [43]. However, due to the
effect of the AMF, the magnetic nanoparticles have uninterrupted
vibration in the hydrogel network, and thus the arrangement of
the magnetic nanoparticles become more loose. It is reasonable
to suggest that an increase of the distance between the molecu-
lar chains lead to a larger space in the hydrogel networks, which
allows water to enter further. This phenomenon can affect the
swelling behavior of the whole system (Fig. 9(c)). As a result, the
mf-NC hydrogels can continue to swell and achieve new swelling
equilibrium to get higher swelling ratio. Furthermore, from the
experimental phenomena, the re-swelling process of the mf-NC
3
hydrogel is irreversible, so it does not de-swell when the AMF is
Fig. 8. (I) The magnetic response testing of hydrogels (b) pure PMOA, (c) mf-NC
1
, (d) mf-NC
2
, (e) mf-NC
3
. (II) The sensing distances between the magnet and the samples
with varying ATFe
3
O
4
content. (III) Hysteresis loop analysis of the mf-NC hydrogels incorporated with various ATFe
3
O
4
additions measured by VSM.
74 Y. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 415 (2012) 6876
Fig. 9. Comparison of the re-swelling ratios (a) and the images (b) of the mf-NC
3
hydrogel measured with and without the application of an AMF (c). Schematic showing the
magnetic response mechanismof the mf-NC hydrogels in the AMF.
halted. Of course, the magnetic response behavior of the mf-NC
hydrogel is relatively slow, which may be related to the magnetic
eld strength, alternating frequency and the content of magnetic
nanoparticles in the hydrogels and so on. This part will be the sub-
ject of a detailed study in the future experiments.
3.2.3. Thermo- and pH-responsive behaviors of the mf-NC
hydrogels
In a recent publication [35], we have demonstrated that the
PMOA terpolymer hydrogel based on MEO
2
MA, OEGMA and AAc
units exhibited both thermo- and pH-responsive behaviors. To
conrm the dual responses of the mf-NC hydrogels, we investi-
gate the effects of temperature and different pH buffer solutions
on the swelling ratios of the samples. Schematic representation
of the mf-NC hydrogels exhibiting stimuli sensitivity in response
to temperature and pH is presented in Fig. 10(a). As previously
reported for PMOA hydrogels [35], this transition can be attributed
to the H-bonding interactions between ethenoxy polar groups
of OEG side chains and water. At temperature below the LCST,
strong H-bonding interactions lead to good solubility, resulting in
higher swelling ratios. When the temperature ascends beyond the
LCST, the conformational transition of OEG side chains decreased
the polarity of ethenoxy groups, and hydration is weakened. The
hydrogels began to shrink, resulting in lower swelling ratios. Data
summarized in Fig. 10(b) showthat the equilibriumswelling ratios
of all hydrogels decrease with increasing temperature from 25

C
to 55

C. The main conclusion that can be deduced fromthis graph

is that the thermo-sensitivity of mf-NC hydrogels is not eliminated
with the incorporation of ATFe
3
O
4
nanoparticles. Fig. 10(c) shows
the pH-dependent swelling behavior of the mf-NC
2
hydrogel at
room temperature (25

C), indicating the transition point of pH at

around 4.5 where the hydrogel networks start to dissociate. This
dissociation occurs in a very narrowpH range. When the pH value
of the buffer solution is above 4.5, the hydrogels begin to swell.
When the pH is below 4.5, the hydrogels can protonate their car-
boxyl moieties of AAc, and the carboxyl moieties form a lot of
hydrogen bonds, which pull back the whole network chain seg-
ments and squeeze more solution out of the hydrogels, resulting in
shrinking. Fromthe above analysis results, the mf-NC hydrogel still
possesses temperature- andpH-sensitivesimultaneously. Thetem-
perature and pH dependent swelling of the hydrogel is reversible,
although the magnetic ATFe
3
O
4
nanoparticles were introduced
into the PMOA system.
3.2.4. Tensile properties of the mf-NC hydrogels
The mechanical properties of the mf-NC hydrogels were stud-
ied by tensile testing. Fig. 11 shows that the tensile strength of
the mf-NC hydrogels increases with increasing of ATFe
3
O
4
con-
tent. When the content of ATFe
3
O
4
increased from 0 to 5%, the
tensile strength doubled. The signicant improvement in mechan-
ical properties can be attributed to reinforcement on the physical
cross-linked PMOA network from the ATFe
3
O
4
clay. Similar rea-
sons have been detailedly discussed in our previous publication on
the PMOA/AT nanocomposite system[31].
Y. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 415 (2012) 6876 75
Fig. 10. (a) Schematic representation of the mf-NC hydrogels exhibiting stimuli sensitivity in response to temperature (Tc is the critical phase transition temperature) and
pH. (b) Changes of swelling ratios of pure PMOA and mf-NC hydrogels with the temperature in the deionized water range from25

C to 55

C (c). The equilibriumswelling

behavior of mf-NC
2
hydrogel at different pH (from1.98 to 10.38) values at 25

C.
Fig. 11. Tensile strength depending on the content of ATFe
3
O
4
.
4. Conclusions
Herein, we have successfully prepared multi-functional
organic/inorganic hybrid hydrogels. Firstly, a simple and effec-
tive method has been developed to decorate the AT with Fe
3
O
4
via electrostatic attraction. The results showed that Fe
3
O
4
nanoparticles were well deposited on the surface of AT and the
ATFe
3
O
4
nanocomposite particles presented the superpara-
magnetic behavior at 300K. Secondly, the magnetic ATFe
3
O
4
nanoparticles were directly incorporated into the dual-responsive
PMOA hydrogel network by in situ free radical polymerization.
It has been demonstrated that the rod-like magnetic ATFe
3
O
4
nanoparticles were well dispersed in the hydrogel matrix. The
magnetic hysteresis loops indicated that the mf-NC hydrogel
exhibited superparamagnetic behavior, and the saturation magne-
tization of that increased with increasing the ATFe
3
O
4
content.
The mf-NC hydrogel can continue to swell in an alternating mag-
netic eld after equilibrium swelling in deionized water. These
results showthat the mf-NC hydrogel can be used in magnetically
controlled release of drugs under the magnetic eld. Despite
the magnetic functionality, the mf-NC hydrogels also possess
considerable temperature/pHsensitivity and excellent mechanical
properties. The unique combination of these multiple sensitivities
in organic/inorganic hybrid hydrogels makes them interesting
candidates for design of articial muscles, biosensors and actuators
and so on.
Acknowledgments
This work was supported by grants from the Program of
Introducing Talents of Discipline to Universities (No. 111-2-04).
76 Y. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 415 (2012) 6876
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