Macromolecular

Full  Paper Materials and Engineering

PVA/Carbon Dot Nanocomposite Hydrogels for

Simple Introduction of Ag Nanoparticles with
Enhanced Antibacterial Activity
Meng Hu, Xiaoyu Gu, Yang Hu,* Yonghong Deng,* Chaoyang Wang*

The introduction of nanomaterials to hydrogels is an effective way to improve the mechan-

ical properties of hydrogels. Herein, carbon nanodot (C-dot) as a new-found excellent nano-
material is first added to polyvinyl alcohol (PVA) hydrogel to prepare PVA/C-dot hydrogel by
freeze–thaw method. The appropriate size and plenty of surface functional groups make
C-dot an ideal nucleating agent for PVA crystallization, which leads to form a denser and
more uniform cross-linked network in PVA hydrogel, and in turn enhance the mechanical
properties of PVA hydrogel. Compared to pure PVA hydrogel, about a 46.4% increase of tensile
strength and 18.5% increase of elongation at break are achieved when the content of C-dot in
PVA/C-dot hydrogel is 2 wt%, suggesting that C-dot can effectively improve the mechanical
properties of PVA hydrogel. Besides, C-dot can endow PVA hydrogel with some new proper-
ties, such as fluorescence and reducibility. Herein, Ag nano-
particles are simply introduced and uniformly dispersed in
PVA hydrogels with the help of reducibility of C-dot, which
can greatly enhance the antibacterial activity of PVA/C-dot
hydrogels, and enlarge their application potential in medical
field.

1. Introduction biosensors, and wound dressings.[1–9] In particular, poly-

Hydrogels, as a kind of soft-wet material that composed
of a large amount of water and 3D networks of polymer
chains, have been widely applied to various biomedical
areas, such as tissue engineering scaffolds, drug car-
riers, and drug release, vehicles, scaffolds for cell cultures,
Dr. M. Hu, Dr. X. Y. Gu, Dr. Y. Hu, Prof. C. Y. Wang
Research Institute of Materials Science
South China University of Technology
Guangzhou 510640, China
E-mail: huyang0303@scau.edu.cn; zhywang@scut.edu.cn
Dr. Y. Hu
College of Materials and Energy
South China Agricultural University
Guangzhou 510642, China
Prof. Y. H. Deng
Department of Materials Science and Engineering
South University of Science and Technology of China
Shenzhen 518055, China
E-mail: yhdeng08@163.com
vinyl alcohol (PVA) hydrogel has been widely studied and
well demonstrated to be an ideal biomaterial due to its
excellent mechanical properties, biocompatibility, and low
water absorption abilities.[10–15] However, when the water
content is higher than 80 wt%, the pure PVA hydrogel pre-
pared by freeze–thaw method could not always keep its
strong mechanical properties,[16,17] which limited its appli-
cations. Fortunately, the addition of the nanomaterials into
PVA hydrogel to form composite hydrogel is a good way to
improve its mechanical properties. Liu and co-workers[18]
incorporated graphene oxide (GO) into PVA to fabricate
GO/PVA composite hydrogel by a freeze–thaw method.
Compared to pure PVA hydrogel, the tensile strength and
compressive strength of GO/PVA composite hydrogel had
increased by 132% and 36%, respectively. Xiong and Pan[19]
successfully prepared nano-hydroxyapatite (nano-HA)/PVA
composite hydrogel with an 87% increase in compressive
strength by addition of nano-HA into PVA hydrogel. Ruan
and co-workers[20] found that the addition of GO could
significantly reinforce the tensile strength and elongation

Macromol. Mater. Eng. 2016, DOI: 10.1002/mame.201600248

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of boron-cross-linked GO/polyvinyl alcohol (B-GO/PVA)
hydrogels. Different from common chemical and physical
hydrogels, PVA hydrogel is usually prepared by freeze–
thaw method, which forms PVA crystal nuclei to act as
physical cross-linking points (because there are strong
hydrogen bonding interactions in PVA crystal nuclei) in
PVA hydrogel.[10–13,21,22] Therefore, the number and distri-
bution of PVA crystal nuclei have great influence on the
mechanical properties of PVA hydrogel.[23,24] As we know,
proper nucleating agent can help form much more crystal
nuclei with uniform dispersion. Therefore, the addition of
appropriate nucleating agent into PVA hydrogel could help
form a denser and more uniform cross-linked network in
PVA hydrogel, which could also enhance the mechanical
properties of PVA hydrogel. In PVA hydrogel, the crystal
nuclei are usually smaller than 10 nm,[24,25] thus the ideal
nucleating agent of PVA should also be smaller than
10 nm, and can strongly interact with PVA chains. Consid-
ering the above factors, most of nanomaterials including
the above-mentioned GO and HA are not the appropriate
nucleating agents for the formation of PVA hydrogels. The
strong physical interaction between PVA and GO/HA, and
the stress transferred from PVA chains to stiff GO/HA is the
main factor for the enhancement of mechanical properties
of GO/PVA or HA/PVA hydrogels.[18]
Carbon nanodot (C-dot) as a newly discovered nanoma-
terial with many exceptional properties, such as low cyto-
toxicity, very good biocompatibility, high fluorescence
quantum yield, stable aqueous dispersion, outstanding
reducibility, and excellent chemical stability[26–30] has
already been widely studied in many fields, such as drug
delivery, cell imaging, sensing, optoelectronic materials,
and catalysis.[29,31–35] Notably, as a kind of new nano-
material with plenty of functional groups (similar to GO
and HA), C-dot could also form strong physical interac-
tion with PVA chains, and thus enhance the mechanical
properties of PVA hydrogel. Besides, the size of majority
C-dot is smaller than 5 nm. As a result, compared to other
nanomaterials (GO and HA), C-dot also acted as nucle-
ating agent in PVA hydrogel, which can further improve
its mechanical properties. Furthermore, the addition of
C-dots into PVA hydrogel could endow the PVA hydrogel
with some new properties, such as fluorescence and
reducibility, which could enlarge the application poten-
tial of PVA hydrogel. Moreover, to the best of our knowl-
edge, the incorporation of C-dots into PVA hydrogel
has not been reported yet. In this study, the PVA/C-dot
hydrogels were successfully prepared by simply freezing
and thawing the mixture aqueous suspension of PVA
and C-dots. The morphology, structure, and mechanical
properties of PVA/C-dot hydrogels were comprehensively
investigated. According to the test results, the probably
reinforcing mechanism of PVA/C-dot hydrogels was pro-
posed. Furthermore, the Ag nanoparticles were simply
Macromol. Mater. Eng. 2016,  DOI: 10.1002/mame.201600248
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introduced and uniformly dispersed into PVA hydrogel by
the reducibility of C-dot, which greatly enhanced its anti-
bacterial property, and in turn enlarged the application
prospect of PVA hydrogel in medical field.
2. Experimental Section
2.1. Materials
PVA (AH-26, alcoholysis degree: 97%–98.8%, polymeriza-
tion degree: 2600) was purchased from Sinopharm Shanghai
Chemical Reagent Co. Ltd. (China). β-Cyclodextrin was obtained
from Aladin Ltd. (China). Hydrochloric acid (HCl) was pro-
vided by Guangzhou Chemical Factory (China). Here, PVA, HCl,
and β-cyclodextrin were analytical grade and used as received
without further purification. Pure water was produced by deioni-
zation and filtration using a Millipore apparatus (resisteivity ≥
18.2 MΩ cm).
2.2. Preparation of C-Dots
C-dots were prepared according to a previously reported
method.[32] Briefly, 5 g β-cyclodextrin was dissolved in 30 mL
concentrated HCl (18–19 wt%), followed by keeping the mixed
solution at 70 °C for 4 h to obtain a brown C-dot suspension. Then,
most of HCl and water were removed by a rotary evaporation
(60 °C), and adjusted the pH to 7–8 with Na2CO3 (2.5 mol L−1). After
that, the neutral brown suspension was centrifuged at 15 000 rpm
for 25 min to separate big particles, and the supernatant was
further dialyzed with a dialysis bag (retained molecular weight:
500 Da) for 24 h to purify the C-dots. Finally, the pure C-dot power
was obtained by freeze-drying the purified C-dot suspension.
2.3. Preparation of PVA/C-Dot Hydrogels
The PVA/C-dot hydrogel was prepared using the freezing–
thawing method. The C-dots were dispersed with deionized water
to a desired concentration (0.05 g mL−1). Here, the PVA/C-dot
hydrogel with 20 wt% PVA (WPVA/Wall) and different C-dot con-
tents had been prepared. Taking the PVA/C-dot hydrogel with
4 wt% (WC-dot/WPVA) C-dot content as an example, 24 g of PVA
power and 19.2 mL of C-dot aqueous dispersion (0.05 g mL−1) were
mixed into 76.8 mL pure water and stirred continuously at 45 °C
for 0.5 h, followed by dissolving PVA at 95 °C and 200 r min−1
stirring for 2 h to obtain a transparent homogeneous PVA/C-dot
suspension. Then, the homogeneous PVA/C-dot suspension was
sealed and kept at 40 °C for removal of air bubbles, and then
were poured between glass slides with 1 mm space. Finally, after
subjecting the PVA/C-dot suspension to repeated freeze–thaw
cycles (a freezing step for 18 h at −18 °C followed by a thawing
step for 6 h at room temperature), the PVA/C-dot hydrogels were
obtained. In this work, the hybrid hydrogels were denoted as
PVA/Cn, where C for C-dots, and the subscript n for the weight
ratio of PVA/C-dot. The concentration of monomer PVA was fixed
at 20 wt%. For example, PVA/C1 meant that the gel consisted of
7.98 g water, 2 g PVA, and 0.02 g C-dots. Without special illustra-
tion, PVA/Cn had through seven freeze–thaw cycles.
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PVA/Carbon Dot Nanocomposite Hydrogels for Simple Introduction of Ag Nanoparticles . . .
2.4. Preparation of PVA/C-Dot-Ag Hydrogels
For preparation of PVA/C-dot-Ag hydrogels, the cylindrical
PVA/C-dot hydrogels with diameter of 1 cm and height of 1 mm
were immersed in AgNO3 (0.05 m) for 5 h in dark until swollen
equilibrium, then the hydrogels were put in sunshine for another
5 h to reduce the Ag+ to Ag nanoparticles in hydrogels by C-dot.
Finally, the obtained PVA/C-dot-Ag hydrogels were immersed in
plenty of pure water at least 5 d with daily change to remove the
residual Ag+.
2.5. Swelling Kinetics
To investigate the swelling kinetics of PVA and PVA/C-dot hydro-
gels, the square samples with diameter of 2 mm and height of
1 mm of different hydrogels were immersed in a large amount of
distilled water at room temperature. At consecutive time inter-
vals, the weight of hydrogel samples at different swelling time
was measured. Before measurement, the sample surfaces were
dried with filter papers to remove the residual water. In order
to reduce the error, every sample was measured at least three
times. The swelling ratios of PVA and PVA/C-dot hydrogels were
calculated according to formula (1)
Qw = (Wswollen − Was-prepared )/Was-prepared
Wswollen and Was-prepared are the weight of the swollen hydrogel
and as-prepared hydrogel, respectively.
2.6. Mechanical Property Measurements
The mechanical properties of the PVA and PVA/C-dot hydrogels
were measured by Shimadzu Auto-graph AG-Xplus 50 N system
at room temperature. The hydrogel samples used for tensile
testing were cut into strips of about 50 mm in length, 10 mm
in breadth, and 1 mm in height using a razor blade. The tensile
strength of the hydrogel samples was measured at a strain rate
of 100 mm min−1. The tensile strain was taken as the length
change related to the initial length and the tensile stress was
evaluated on the cross section of the initial sample.
2.7. Antibacterial Measurement
The antibacterial performance of PVA/C-dot-Ag hydrogels was
investigated by disc diffusion method.[36] In this experiment,
Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were
taken as the test bacteria. The concentration of two test strains
was about 104–105 CFU mL−1. The test samples (PVA/C-dot-Ag
hydrogels) and the control samples (PVA hydrogels without Ag
nanoparticle) were cut into small discs with 10 mm in diameter
and 1 mm in thickness, and the antimicrobial activity was tested
using modified agar diffusion assay (disc test).[37] The surface of
samples was examined after incubation at 37 °C for predeter-
mined time intervals. The surface of the hydrogel discs was kept
clean (without colonies) on the plates and recorded as an inhibi-
tion against the microbial species.
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2.8. Characterization
Transmission electron microscope (TEM, JEOL JEM-2100F) was
used to characterize the particle diameter and morphology of
the obtained C-dots, with an accelerating voltage of 200 kV.
German Vector-33 IR instrument was used to obtain the Fou-
rier transform infrared (FT-IR) spectra of C-dots and PVA/C-dot
hydrogel in the range of 400–4000 cm−1 at room temperature.
The UV–vis absorption spectroscopy of PVA/C-dot-Ag hydrogels
and the transmittance of PVA and PVA/C-dot hydrogels with
different freezing–thawing times at wavelength λ = 600 nm
were carried out on Hitachi U-3010 UV–vis spectrophotometer
(Japan). Netzsch differential scanning calorimetry (DSC) 204 F1
was used to assess the thermal properties (including glass tran-
sition temperature (Tg), melting temperature (Tm), and heat of
melting (ΔHm)) of dry PVA and PVA/C-dot hydrogels, calorimeter
on heating from 20 to 250 °C at the rate of 10 °C min−1 under
nitrogen protection. The Tg values of the PVA and PVA/C-dot
hydrogels were directly determined from inflection point of the
DSC curves, while the Tm and ΔHm values of the PVA and PVA/C-
dot hydrogels were directly determined from the melting peak of
the DSC curves. The crystallinity of the PVA and PVA/C-dot hydro-
gels was calculated by dividing the ΔHm of hydrogel samples by
the ΔHm of melting of a 100% crystalline PVA (138.6 J g−1).[38]
Thermal stability of PVA, PVA/C-dot, and PVA/C-dot-Ag hydrogels
(1) was examined by NETZSCH TG 209F3 instrument, heating from
40 to 700 °C at the rate of 10 °C min−1 under a nitrogen atmos-
phere. Before DSC and TG testing, the pure PVA and PVA/C-dot
hydrogels were first sliced into squares and dried in an oven at
60 °C for 3 d. The crystallinity structure and grain size of pure
PVA and PVA/C-dot hydrogels were measured by X-ray diffrac-
tion (XRD), using an X’pert PRO diffractometer (40 kV and 40 mA)
equipped with a Cu Kα radiation (wavelength 0.154 nm) at room
temperature. The crystallinity (Xc) of different hydrogels was cal-
culated by Equation (2)
X c = APVA /A0 × 100% (2)
APVA is the PVA crystalline peak area and A0 presents the total
area that is attributed to PVA.[39,40]
3. Results and Discussion
3.1. Structure of PVA/C-Dot Hydrogels
TEM image of the C-dots demonstrated that the C-dots
were spherical nanoparticles with narrow particle size dis-
tribution of 2.77 ± 0.8 nm, as shown in Figure 1a,b (about
100 particles had been counted). Figure S1a,b (Supporting
Information) showed that the obtained C-dots could be
dispersed uniformly in aqueous solution for a long time
even at high concentration (50 mg mL−1). Besides, the
abundant surface functional groups (such as hydroxyl,
carbonyl, and epoxy group) of C-dots could interact with
PVA chains to form strong hydrogen bonds, which was
in favor of C-dots dispersing in PVA aqueous solution. As
shown in Figure S1c,d (Supporting Information), even
3
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crystals.[41,42] The characteristic peaks

a b
45
40 of PVA crystal were nearly not changed
35
5 nm 30
in dried PVA/C-dot hydrogel, indicating

Intensity (%)
25 that C-dot would not influence the
20 crystal structure of PVA. From the XRD
15 curves, the crystallinity (Xc) of PVA and
10 PVA/C-dot hydrogels could be calcu-
5
lated. As shown in Figure 2c, the crystal-
50 nm 0
1.5 2.0 2.5 3.0 3.5 4.0 4.5 linity of C-dot/PVA hydrogel was higher
Size (nm) than pure PVA hydrogel, and increased
Figure 1.  a) TEM image and b) size histogram (counting at least 100 particles) of synthe- along with the increase in the C-dot
sized C-dots. The inset in (a) is the high-resolution TEM image of C-dot. content, indicating that the addition of
C-dots into PVA hydrogel could increase
the concentration of PVA aqueous solution was as high the crystallinity of PVA.
as 20 wt%, 4 wt% C-dot could be well dispersed in PVA To illuminate the interaction between C-dots and PVA
aqueous solution and form a kind of uniform and trans- chains, FTIR spectra of C-dot, dried PVA hydrogel, and the
parent mixture suspension. Moreover, the mixture suspen- dried PVA/C-dot composites hydrogel were measured. As
sion could emit 520 nm green fluorescence under 365 nm shown in Figure 3 and Figure S3 (Supporting Informa-
(Figure S1d,e, Supporting Information), further demon- tion), the spectra of C-dots exhibited strong OH, CO
strating that the C-dots could uniformly disperse in PVA stretching vibrations and CO (in the COC group)
aqueous solution without agglomeration. symmetric stretching vibrations peaks at 3365, 1641, and
Different from other carbon material composite hydro- 1028 cm−1, respectively, which indicated that there were
gels which exhibited opaque black when the content of
carbon materials is higher than 1%,[21–23] the PVA/C-dot
hydrogels prepared by the freeze–thaw method were a
semitransparent, even the content of C-dot was as high
Intensiy (a.u.)

PVA/C4
as 4%. Figure S2a,b (Supporting Information) showed
PVA/C2
that the transmittance of PVA/C-dot hydrogels was still PVA/C1

more than 40% after seven times freeze–thaw, which 26.8 PVA/C0.5

was nearly the same as pure PVA hydrogel, proving that 41 PVA
18.6 19.6 C-dot
C-dots were dispersed very well in PVA hydrogel, and did
not influence the transmittance of PVA hydrogel. Besides, 0 20 40 60 80
2 θ (Degree)
owing to the degree of crystalline in hydrogels increased
b 19.6
along with freeze–thaw times, the light scattering of the
hydrogel would increase. As a result, the transmittance of 40.7 PVA/C4
Intensiy (a.u.)

PVA and PVA/C-dot hydrogels decreased along with the PVA/C2

freeze–thaw times (Figure S2a, Supporting Information). PVA/C1

As we mentioned above that C-dots could be an ideal PVA/C0.5

nucleating agent for PVA, which would influence the PVA
crystal degree of PVA hydrogel. To explore the effect of
C-dots on the degree of crystallinity of PVA hydrogel, 0 20 40 60
XRD testing of the PVA and C-dot/PVA hydrogels was 2 θ (Degree)
46
performed. As shown in Figure 2a,b, for the as-prepared
c
hydrogels (Figure 2a), two peaks of water (at 28° and 41°)
Crystallinity (%)

44
were very clearly observed, but the crystallization peak
of PVA at 19.6° was not obvious. This could be ascribed to 42
the overlap of strong water signals and weak PVA crystal
signals at the low content of polymer.[23] Hence, in this 40
experiment, the crystallinity of PVA and PVA/C-dot hydro-
gels was estimated from the corresponding dried hydro- 38
0 1 2 3 4
gels instead. Figure 2b showed that the dried PVA and C-dot (Wt %)
PVA/C-dot hydrogels appeared the same characteristic Figure 2.  The XRD patterns of a) as-prepared and b) dried PVA and
peak of the crystal at 2θ, 19.6° (strongest), 22.9°, and 40.8° PVA/C-dot hydrogels; c) crystallinity of dried PVA and PVA/C-dot
corresponding to the (101), (200), and (102) planes of PVA hydrogels.

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C-dots
a
PVA 1641
1028 PVA
Intensity (a.u.)

3365 PVA/C1
PVA/C0.5
PVA/C2 1657
PVA/C1
3285

Endo
1653
PVA/C2

3274 PVA/C4
3272

3500 2800 2100 1400 700

-1 25 50 75 100
Wavenumber (cm ) Temperature (o C)
Figure 3.  FTIR spectra of C-dot powder, dried PVA, and PVA/C-dot
hydrogels. b PVA
PVA/C0.5

plenty of hydroxyl, carboxyl, and epoxy groups on C-dot PVA/C1

surface. Besides, the OH stretching vibrations peak at PVA/C2

3365 cm−1 of C-dot and 3285 cm−1 of dried PVA hydrogel

Endo
PVA/C4
shifted to lower wavenumbers for the dried PVA/C-dot
hydrogel (at 3272 and 3274 cm−1), suggesting that the
strong hydrogen bonds were formed between PVA chains
and C-dots. Furthermore, for the dried PVA/C-dot hydrogel 150 175 200 225 250
with 2 and 4 wt% C-dot contents, the CO stretching Temperature (o C)
vibrations peak at 1641 cm−1 of C-dot shifted to 1657 Figure 4.  DSC curves of PVA and PVA/C-dot hydrogels: a) glass
and 1653 cm−1, respectively, which indicated the forma- transition temperature (Tg) and b) melting point (Tm).
tion of hydrogen bonding between the carboxyl groups
of C-dot surface and the hydroxyl groups of PVA. All the hydrogels. Figure 4b showed only one strong endothermic
results confirmed the presence of the strong hydrogen or exothermic peak for both dried pure PVA and PVA/
bonds between the hydroxyl groups of PVA chains and the C-dot composite hydrogels in the range between 180 and
oxygen-containing groups (hydroxyl and carboxyl groups) 240 °C, indicating that the addition of C-dot nanoparticles
of C-dot surface in PVA/C-dot hydrogels. would not affect the crystal of PVA hydrogels, which was
To investigate the glass transition temperature (Tg) and consistent with the XRD test result (Figure 2). However,
further analyze the crystallization behavior of PVA/C-dot the melting point (Tm) of PVA/C-dot composite hydrogels
hydrogels, the DSC analysis of dried pure PVA and PVA/ was lower than that of the dried pure PVA hydrogel, and
C-dot composites hydrogels was performed. As shown decreased along with the increase of C-dot content. For
in Figure 4 and Table 1, the Tg of pure PVA hydrogel was example, the Tm of PVA/C4 was just about 215.4 °C, which
about 62.7 °C, while that of the dried PVA/C-dot com- was lower (4.5 °C) than that of dried pure PVA hydrogel
posite hydrogels was much lower. For example, the Tg of (Table 1). This phenomenon was similar to other nano-
PVA/C-dot hydrogel prepared with 4 wt% C-dot content particle/PVA composite film,[43] because the crystals
(PVA/C4) was just about 55.8 °C, which was 6.9 °C lower formed on C-dots were defective, leading to the decrease
than that of dried pure PVA hydrogel. This phenomenon of Tm. Moreover, the crystallinity (Xc) of all samples could
was different from the previously reported nanoparticle/ be calculated from the endothermic or exothermic peak
polymer composite hydrogels, whose glass transition of DSC with Equation (3)
temperature (Tg) was almost independent of the nano-
particle content.[21–23,45] This maybe because the spherical Table 1.  Parameters obtained from DSC curves of pure PVA and
C-dot was more flexible than the flake (such as clay and the PVA/Cn hydrogels.
graphene) and linear (such as nanocellulose) nanopar-
ticles in hydrogel networks, which could bring larger Sample Enthalpy Melting point XPVA Tg
space for free movement of PVA chains. Therefore, the [J g−1] [°C] [%] [°C]
PVA chains in PVA/C-dot composite hydrogel were free, PVA 56.51 219.9 40.8 62.7
high flexible, and took on nearly random conformations PVA/C0.5 59.75 218.5 43.1 62.3
around the C-dots. Here, Tg decreased obviously along
PVA/C1 62.15 216.2 44.8 59.8
with the increase of C-dot content, fully demonstrating
that the addition of C-dot nanoparticles greatly improved PVA/C2 63.36 217.4 45.7 57.6
the mobility and flexibility of PVA chains in the PVA/C-dot PVA/C4 59.62 215.4 43 55.8

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X c = H m /H 0 (3) bonding interaction was formed between PVA chains and

Hm is the measured melting enthalpy of dried PVA and
PVA/C-dot composite hydrogels (from DSC) and H0 is the
enthalpy of pure PVA crystal (138.6 J g−1).[44,45] As shown
in Table 1, compared to dried pure PVA hydrogel, the crys-
tallinity of PVA in PVA/C-dot composite hydrogels was
increased. The crystallinity of dried pure PVA hydrogel
was about 40.8%, while the crystallinity of dried PVA/C-dot
hydrogel prepared with 2 wt% C-dot content
(PVA/C2) was about 45.7%, which was 4.9% higher than
that of dried pure PVA hydrogel. This phenomenon was
very different from the reported PVA/nanoparticle hydro-
gels and films. For example, no obvious change of PVA
crystallinity was observed in PVA/GO, PVA/clay, and
PVA/nanodiamond (ND) composite hydrogels or
films.[21,43,44,46] That was because although there was
strong hydrogen bond interaction between PVA chains
and graphene, clay and nanodiamond, their big sizes lim-
ited them to be an ideal nucleating agent for PVA (the size
of graphene was micrometers, the size of clay was about
20 nm, and the size of nanodiamond was about 10 nm,
while the size of PVA crystal nucleus was always smaller
than 10 nm),[21,27,28,43] causing that the crystallinity of PVA
was not obviously changed. While the strong hydrogen
C-dots, and the smaller nano-size (in this study, the average
size of C-dots was smaller than 3 nm) makes spherical
C-dot an ideal nucleating agent for PVA, thus the crystal-
linity of PVA in PVA/C-dot hydrogels had been increased,
which was also consistent with the above XRD test result.
The scanning electron microscopy (SEM) images of
lyophilized pure PVA and PVA/C-dot composite hydro-
gels are shown in Figure S4 (Supporting Information).
Both the lyophilized pure PVA and PVA/C-dot composite
hydrogels exhibited uniform microporous structure.
However, the lyophilized PVA/C-dot composite hydrogels
exhibited more intensive and smaller microporous struc-
tures than that of the lyophilized pure PVA hydrogel. That
was because the addition of C-dots led to an increase in
the cross-linking density (XRD and DSC indicating that
the crystallinity in PVA/C-dot composites hydrogels was
increased) to produce a denser microstructure.
3.2. Properties of PVA/C-Dot Hydrogels
To investigate the influence of C-dots on PVA hydrogel
mechanical property, the mechanical properties of pure
PVA and PVA/C-dot hydrogels with different freeze–thaw
cycles had been tested. As shown in Figure 5, Figure S5

Figure 5.  Mechanical properties of PVA and PVA/C-dot composite hydrogels: a) tensile strength, b) elongation at break, c) Young’s modulus,
and d) fracture energy as a function of freeze–thaw cycle time.

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PVA/Carbon Dot Nanocomposite Hydrogels for Simple Introduction of Ag Nanoparticles . . . Materials and Engineering
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Table 2.  Mechanical properties of the as-prepared PVA and PVA/C-dot hydrogels after seven freeze–thaw cycle times.

Sample (PVA/Cn) Tensile strength Elongation at break Young’s modulus Fracture energy
[MPa] [%] [KPa] [J m−2]
PVA 0.56 ± 0.034 271 ± 21 113 ± 8 733 ± 71
PVA/C0.5 0.67 ± 0.080 315 ± 28 101 ± 6 808 ± 106
PVA/C1 0.75 ± 0.034 310 ± 15 108 ± 8 926 ± 68
PVA/C2 0.82 ± 0.045 321 ± 24 105 ± 9 1052 ± 112
PVA/C4 0.65 ± 0.060 305 ± 22 108 ± 7 840 ± 89

(Supporting Information), and Table 2, similar to the
common PVA hydrogel prepared by freeze–thaw method,
the tensile strength, Young’s modulus, and fracture energy
of the as-prepared PVA and PVA/C-dot composite hydrogels
increased along with the increase in freeze–thaw cycles.
After seven freeze–thaw cycles, the optimal mechanical
properties of the as-prepared PVA and PVA/C-dot hydro-
gels were obtained. And the mechanical properties of the
PVA/C-dot composite hydrogel remarkably increased with
the addition of C-dots. As shown in Table 2, after seven
freeze–thaw cycles, the PVA/C-dot hydrogel prepared with
2 wt% C-dot content (PVA/C2) showed a tensile strength of
0.82 ± 0.045 MPa, which was about 46.4% higher than that
of pure PVA hydrogel (0.56 ± 0.034 MPa). Besides, the elon-
gation at break of PVA/C2 was 321 ± 24%, which was about
18.5% higher than that of pure PVA hydrogel. And because
of the increase of tensile strength and elongation at
break, the fracture energy of PVA/C2 (1052 ± 112 J m2) was
also about 43.5% higher than that of pure PVA hydrogel
(733 ± 71 J m2). All above mechanical test results suggested
that the addition of C-dots could effectively reinforce the
mechanical properties of PVA hydrogel.
Some literature have reported that the addition of
nanomaterials, such as GO and carbon nanotubes (NTs),
can greatly improve the mechanical properties of PVA
hydrogels.[21,47,48] And for those hybrid hydrogels, the
mechanical properties were mainly enhanced due to the
following two aspects: first, the high tensile modulus
and strength of nanomaterials could
endure high load; second, the strong
hydrogen bonds present between PVA
chains and nanomaterials. The load
could be effectively transferred from
the PVA matrix to the nanomaterials,
which enhanced the mechanical prop-
erties of PVA hydrogels.[21,47,48] How-
ever, different from NTs and GO, C-dots
did not possess extremely high ten-
sile modulus and strength,[47,48] which
meant the main factor for the enhance-
ment of the mechanical properties
in PVA/C-dot hydrogel was not load
transfer. As we mentioned above, in Figure 6.  The schematic forming model of PVA/C-dot hydrogels.
PVA hydrogel, the PVA chains were cross-linked by PVA
crystal nuclei and finally formed intact 3D network.[24]
Therefore, the degree of crystallinity and the distribu-
tion of PVA crystal nuclei had a significant impact on the
mechanical properties of PVA hydrogels.[26] The uniform
distribution of the denser crystal nuclei (cross-linking
points) could lead to better mechanical properties of PVA
hydrogel. According to the test results of XRD and DSC,
C-dots could act as an ideal nucleating agent to greatly
increase the crystallinity (denser crystal nucleus) of
PVA/C-dot hydrogels. Therefore, we speculated that the
enhancement of the mechanical properties of PVA/C-
dot hydrogel was mainly ascribed to the fact that the
denser crystal nuclei (cross-link points) of PVA increased
with the addition of C-dots. After the PVA solution was
mixed with C-dots, many PVA chains would be adsorbed
and arranged on C-dot surfaces because of the strong
hydrogen bonding interaction, which was in favor of
PVA crystallization. More important, the proper nano-
size of C-dot could be used as an ideal nucleating agent
for PVA. In freeze–thaw process, some C-dots would act
as nucleating agent of PVA to assist in forming more
PVA crystal nuclei, and uniformly distributed in PVA/C-
dot hydrogel (Figure 6), which improved the mechan-
ical properties of PVA/C-dot hydrogel. Moreover, C-dots
could also act as lubricant in stretching process, which
led to the increase in the elongation at break of PVA/C-
dot hydrogel.[49]

Macromol. Mater. Eng. 2016,  DOI: 10.1002/mame.201600248

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Figure 7.  Swelling ratio of the as-prepared PVA and PVA/C-dot
hydrogels. The inset is the partial enlarged view.
To further investigate the influence of C-dots on PVA
hydrogel, the swelling behavior of PVA and PVA/C-dot
hydrogels had been measured. As shown in Figure 7,
the swelling ratio of both PVA and PVA/C-dot hydrogels
increased along with the swelling time, and reached the
swelling equilibrium within 300 min, indicating that the
addition of C-dots did not influence the swelling rate of
PVA hydrogel. However, the swelling ratio of PVA/C-dot
hydrogel at swelling equilibrium condition was smaller
than that of PVA hydrogel. This might be because the
addition of C-dots led to the increase of the crystalline
degree (cross-linking point) of PVA/C-dot, which lim-
ited the stretching of PVA chains, and in turn led to the
decrease in the swelling ratio of PVA/C-dot.
3.3. Introduction of Ag Nanoparticles
Significantly, the addition of C-dots not only improved
the mechanical properties of PVA hydrogel, but also
endowed the PVA hydrogel with some new properties,
such as fluorescence and reducibility. As reported, hydro-
gels were widely used in medical field. Especially, they
could act as wet dressings and drug delivery for wound
healing. Because the bacterial infection is the main cause
of wound infection, the antibacterial property is important
for hydrogel used in medical field.[50,51] Among various
antimicrobial agents, silver is common and well-studied
due to its wide spread antimicrobial spectrum.[42] Herein,
taking the advantage of the reducibility of C-dots, PVA/C-
dot hydrogel could adsorb Ag+ and directly reduce Ag+
to Ag nanoparticle without any other reducing agent,
which was more convenient, economic, and green than
other methods (introducing Ag nanoparticle in hydrogel).
Besides, as we have reported,[32] the Ag+ could be restored
to Ag nanoparticles and fixed on C-dot surface, which
could ensure the Ag nanoparticles well dispersed in
Macromol. Mater. Eng. 2016,  DOI: 10.1002/mame.201600248
8 © 2016  WILEY-VCH Verlag GmbH &  Co.  KGaA, Weinheim
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M. Hu et al.
PVA/C-dot hydrogel (because C-dots could be well dispersed
in PVA hydrogel) without any other dispersing agents. As
shown in Figure S6a (Supporting Information), after the
PVA/C2 swelling in different concentrations of AgNO3 solu-
tion for 5 h, followed by light reduction for 5 h, the color
of PVA/C-dot hydrogel changed to brown or brown black,
indicating that Ag nanoparticles were formed in PVA/C-dot
hydrogel. Besides, the UV–vis absorption spectrum of the
treated PVA/C-dot hydrogel (Figure 8a) showed obviously
Ag nanoparticle absorption peak at 425 nm, further dem-
onstrating that the Ag+ had been successfully restored to
Ag nanoparticles and uniformly dispersed in PVA hydrogel.
Figure 8a also showed that the absorption peak at 425 nm
of treated PVA/C-dot hydrogel decreased when the con-
centration of AgNO3 solution was higher than 0.05 m.
That may be because when the concentration of AgNO3
was too high, the swelling ratio of PVA/C-dot hydrogel
would be seriously decreased, which inhibited the adsorp-
tion of the AgNO3 for the PVA/C-dot hydrogel, and then led
to the decrease in the concentration of Ag nanoparticles
in PVA/C-dot hydrogel. Figure 8b showed that the absorp-
tion peak at 425 nm of PVA/C-dot hydrogel with various
C-dot contents (after swelling in 0.05 m AgNO3 solution
for 5 h, followed by light reduction for 5 h) increased
along with the increase of C-dot content, while the PVA
hydrogel without C-dot did not show any absorption peak
at 425 nm, confirming that the addition of C-dots not only
0.025M 423
a
0.05M
Absorbance (%)
0.1M
0.25M
0.5M
300 400 500 600 700
Wavenumber (nm)
423
b PVA/C4
Absorbance (%)
PVA/C2
PVA/C1
PVA/C0.5
PVA
300 400 500 600 700
Wavenumber (nm)
Figure 8.  UV–vis absorption spectroscopy of PVA and PVA/C-dot
hydrogels: a) UV–vis absorption spectroscopy of the different con-
centration AgNO3-treated PVA/C2 hydrogels; b) UV–vis absorption
spectroscopy of the 0.05 m AgNO3-treated PVA and PVA/C-dot
(with various C-dot contents) hydrogels.
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 Macromolecular
PVA/Carbon Dot Nanocomposite Hydrogels for Simple Introduction of Ag Nanoparticles . . . Materials and Engineering
www.mme-journal.de

hydrogel obviously shifted to higher

temperature. That might be because
Ag had very high thermal stability, the
uniformly dispersing Ag nanoparti-
cles could effectively prevent the heat
transfer between PVA chains, leading to
the great increase in the decomposition
temperature of the PVA/C2-Ag hydrogel.
Moreover, through Tg result, the content
of Ag nanoparticles could be calculated
by formula (4)

WAg = WPVA/C-dot-Ag − WPVA/C-dot (4)

Figure 9.  a) SEM images of dried 0.05 m AgNO3-treated PVA/C2 hydrogels (PVA/C2-Ag);
b) distribution of Ag in PVA/C2-Ag hydrogel.
improved the mechanical properties of PVA hydrogel, but
also could act as reductant to introduce Ag nanoparticles
into hydrogel. Besides, Figure S6b (Supporting Informa-
tion) showed that the color of PVA/C-dot hydrogels with
various C-dot contents also changed to brown, because
the absorbed Ag+ could be restored to Ag nanoparticles.
Furthermore, compared to the PVA/C2 hydrogel, the XRD
test result of the AgNO3 (0.05 m) treated PVA/C2 hydrogel
(Figure S7, Supporting Information) showed a new peak at
38.2°, which correspond to the (111) diffraction of metallic
Ag,[43,52,53] and thus further confirmed that Ag nanoparticle
had been introduced into PVA/C2 hydrogel by the reduc-
ibility of C-dots. Particularly, the XRD test result of the
AgNO3-treated PVA/C2 hydrogel did not show the other
characteristic diffraction peaks of metallic Ag (peaks at
44.2°, 64.5°, and 77.5° that correspond to the (200), (220),
and (311)),[53] because, the content of Ag nanoparticle was
very low compared to PVA crystallization, and the weaker
characteristic diffraction peaks of metallic Ag were over-
lapped by the strong PVA crystal signals.
SEM photos of PVA/C2-Ag hydrogels are shown in
WAg is the content of Ag0 nano-
particles, WPVA/C-dot-Ag is the residual
mass of PVA/C-dot-Ag hydrogel, and WPVA/C-dot is the
residual mass of PVA/C-dot hydrogel. As shown in
Figure 10, the residual weights of PVA/C2-Ag and
PVA/C2 hydrogels were about 6.32 and 5.4 wt%, respec-
tively. Therefore, the content of Ag nanoparticles in PVA/
C2-Ag hydrogel was about 0.92 wt%.
3.4. Antibacterial Performance of PVA/C-Dot-Ag
Hydrogels
In order to investigate whether the PVA/C-dot-Ag hydrogel
had good antibacterial activity or not, the antibacterial
activities of PVA and PVA/C-dot-Ag hydrogels with various
C-dot contents had been determined by the disc method.
Figure 11 showed that the antibacterial activities of var-
ious hydrogels against E. coli and S. aureus determined
by the disc method. It could be obviously seen that after
cultivating for 72 h the E. coli and S. aureus colonies were
100
Residual Mass (wt%)

Figure 9. To further confirm that Ag nanoparticles

were uniformly dispersed in PVA/C2-Ag hydrogel, the
distribution of Ag element in the hydrogel had been 75
measured by EDS mapping. As shown in Figure 9b,
PVA/C2-Ag
R e s id u a l M a s s (w t% )

the mapping image showed that the Ag element was

uniformly dispersed in PVA/C2-Ag hydrogel, indi- 50
10
cating uniform dispersion of Ag nanoparticles in PVA/C2
PVA/C2 -Ag
PVA/C2-Ag hydrogel. Besides, the EDS result (Figure S8,
Supporting Information) showed that the content of Ag 25 PVA/C2
PVA
5 PVA
nanoparticles was about 0.5 wt%. 450 500 550 600 650
The TG curves of the PVA, PVA/C2, and PVA/C2-Ag Temperature (oC)

hydrogel are presented in Figure 10. The TG curves for 0

0 150 300 450 600
PVA/C2 was almost the same as that of pure PVA, indi- o
cating that the addition of C-dots would not influence the Temperature ( C)
thermostability of PVA hydrogel. However, when the Ag Figure 10.  a) TG curves of dried PVA hydrogel, PVA/C2 hydrogel,
nanoparticles had been introduced into PVA/C2 hydrogel, and PVA/C2-Ag hydrogel (after treated in 0.05 m AgNO3). b) The
the decomposition temperature of the PVA/C2-Ag inset is the partial enlarged view.

Macromol. Mater. Eng. 2016,  DOI: 10.1002/mame.201600248

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 Macromolecular
Materials and Engineering
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Figure 11.  Photographs of bacterial colonies formed by a) S. aureus
and b) E. coli cells treated with PVA and PVA/C-dot-Ag hydrogels
(treated in 0.05 m AgNO3).
grown on the pure PVA hydrogel surface, indicating that
pure PVA hydrogels have poor antibacterial activity against
E. coli and S. aureus, which was consistent with the results
reported elsewhere.[44,50] However, compared with pure
PVA hydrogel, no obvious E. coli and S. aureus colonies
could be observed on the surface of PVA/C-dot-Ag hydro-
gels (with various C-dot contents), demonstrating that the
introduction of Ag nanoparticles could greatly enhance the
antibacterial activities of PVA hydrogel.
4. Conclusions
In summary, we successfully prepared a novel PVA/C-dot
hydrogel with excellent mechanical properties by adding
C-dots into PVA hydrogel. The test results of TEM, FTIR,
XRD, and DSC indicated that the proper size of C-dots and
the strong hydrogen-bond interaction between PVA chains
and C-dots made C-dots an ideal nucleating agent for
PVA crystallization in freeze–thaw process, which greatly
increased the crystallization degree (cross-link point) of
PVA/C-dot hydrogel. As a result, compared with the pure
PVA hydrogel, the tensile strength of PVA/C2 hydrogel was
increased by about 41.4%. Besides, C-dots could also act as
Macromol. Mater. Eng. 2016,  DOI: 10.1002/mame.201600248
10 © 2016  WILEY-VCH Verlag GmbH &  Co.  KGaA, Weinheim
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M. Hu et al.
lubricant in stretching process, leading to the elongation at
break of PVA/C2 hydrogel about 18.5% higher than that of
pure PVA hydrogel. Moreover, taking the advantage of the
reducibility of C-dots, the Ag nanoparticles could be intro-
duced and uniformly dispersed in PVA hydrogel by a very
simple method, which enhanced the antibacterial activity
of PVA/C-dot hydrogel, and thus enlarged the potential
application in medical field of PVA hydrogel.
Supporting Information
Supporting Information is available from the Wiley Online
Library or from the author.
Acknowledgements: This work was financially supported by the
National Natural Science Foundation of China (21274046 and
21474032), the National Natural Basic Research Program of China
(973 Program, 2012CB821500), and the Fundamental Research
Funds for the Central Universities (2015ZM158).
Received: May 25, 2016; Revised: July 19, 2016; Published online: ;
DOI: 10.1002/mame.201600248
Keywords: antibacterial activity; carbon nanodots; hydrogels;
nanocomposites; PVA
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