Nano Ag loaded PVA nano-fibrous mats for skin applications
Thi-Hiep Nguyen,1 Young-Hee Kim,2 Ho-Yeon Song,2 Byong-Taek Lee1
1
Department of Biomedical Engineering and Materials, College of Medicine Soonchunhyang University,
Cheonan 330-090, Korea
2
Department of Immunology, College of Medicine, Soonchunhyang University, Cheonan 330-090, Korea
Received 14 March 2010; revised 26 June 2010; accepted 1 July 2010
Published online 17 November 2010 in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/jbm.b.31756
Abstract: Silver nano-particles (Ag NPs) loaded polyvinyl
alcohol (PVA) electro-spun fibers were fabricated using a
combination of microwave-heated and electro-spinning meth-
ods for wound healing. A thermic process was then applied
to resurface and increase the number of the Ag NPs on the
surface of the PVA fiber. The diameter of the Ag NPs loaded
electrospun PVA (PVA-Ag) mats were between 100 and
500 nm after heat treatments at different temperatures. When
samples were subjected to 60 s of microwave irradiation and
INTRODUCTION
Wound healing is a complex process that includes rebuild-
ing the structure and functions of the skin. However, bacte-
rial overgrowth and infection disrupt this process; thus,
there is a need to develop an artificial matrix that can
promote wound healing and prevent microbial infection.
In this study, we fabricated silver nano-particles (Ag
NPs) loaded electrospun PVA mats (PVA-Ag mats) using a
combination of electro-spinning microwave and heat treat-
ments. Ag NPs resurfaced on the surface of the PVA fibers
by a thermic process. This mat has four primary advantages
for skin applications: (1) Silver (Ag) and its compounds
have been known to have extraordinary bacterium-inhibi-
tory and bactericidal properties.1–6 The silver ion has been
shown to exhibit broad-spectrum biocidal activity toward
many different bacteria, fungi, and viruses5,7 and is believed
to be the active component in silver-based antimicrobials. In
addition, Ag has low toxicity toward mammalian cells.7
Because of these benefits, Ag has been widely studied as a
coating material on particular medical devices, such as
indwelling catheters, wound dressing, etc.8–10 However, as
reported by Kim et al., Ag ions (or its components) possess
limited use as an antimicrobial agent for several reasons.4
These limitations can be overcome through the use of Ag
NPs, which enhance the antimicrobial effect. (2) PVA is a
strong host material for metal, due to its excellent thermo-
stability and chemical resistance.11,12 Moreover, PVA is non-
toxic, has high mechanical stability and is degradable in
human environments. Furthermore, PVA contains alcohol
groups that can reduce Agþ to Ag0 without the need for a
reductant as reported by Pal et al.13,14 In addition, PVA is a
Correspondence to: B.-T. Lee; e-mail: lbt@sch.ac.kr
Contract grant sponsor: National Research Foundation of Korea (NRF); contract grant number: 2009-0092808
V
C 2010 WILEY PERIODICALS, INC.
150
C heat treatment, the maximum number of 50–100 nm
Ag NPs resurfaced on the PVA nano-fiber. The nano mats
significantly inhibited E. coli (gram-positive) and S. aureus
(gram-negative) bacteria and displayed high mechanical
stability (>45 MPa). V
C 2010 Wiley Periodicals, Inc. J Biomed Mater
Res Part B: Appl Biomater 96B: 225–233, 2011.
Key Words: antimicrobial, tissue engineering, wound healing
cost-effective reductant agent. (3) Electro-spinning is the
simplest method to fabricate a continuous fiber with a small
diameter (nano-fibers), a high surface area, small pore size,
and good mechanical properties.15,16 (4) Microwave irradia-
tion is considered as a highly efficient method for the fabri-
cation of nano-metals. Furthermore, this technique is envi-
ronmentally friendly (or ‘‘green’’), and is faster, simpler and
more economical than conventional methods12,14 such as
the chemical reduction of NaBH4.17 Therefore, due to the
advantages described above, a PVA-Ag mat was fabricated in
this study and its potential use in wound dressing16 and
antimicrobial applications was investigated.18 However,
when this approach was used, Ag NPs were dispersed inside
the electro-spun PVA fiber, which limited the antimicrobial
activity of the fiber. Therefore, to resurface Ag NPs on the
PVA nano-fibers, a heat treatment process was used. This
process was different from the method used by Hong et al.,
where a microwave step was employed instead of UV irradi-
ation. Moreover, we found that several more nano-particles
were homogeneously dispersed on the surface when the
heat treatment step was conducted at 150
C. The presence
of Ag NPs was confirmed by UV-Vis, XRD, scanning electron
microscopy (SEM), and transmission electron microscopy
(TEM). Interactions between PVA and Ag NPs were exam-
ined by FT-IR. The thermal-crystalline properties of the mat
were assessed by DSC. In addition, the mechanical tests
demonstrated that the mat had high mechanical stress,
which is important for wound healing applications. The anti-
bacterial test showed that the mats had high antimicrobial
activities against both Gram-positive and Gram-negative,
which is imperatvie to decrease infection during the wound
225
healing process. In this study, we demonstrated that the
PVA-Ag mat not only had strong mechanical properties, but
also displayed key antimicrobial activities that are necessary
to reduce and eliminate the risk of infection.
EXPERIMENTAL
Materials
Polyvinyl alcohol (PVA, full hydrolyzed) and AgNO3 (99,998
per cent) were purchased from Aldrich, USA.
Preparation of Ag NPs loaded electrospun PVA
mats through the combination of microwave
and electro-spinning methods
We fabricated PVA-Ag mats from a PVA solution containing
Ag NPs. This suspension was synthesized using a PVA solu-
tion that contained AgNO3 that had been microwave irradi-
ated. First, 12 Wt % PVA in distilled water was prepared at
80
C. Then, an aqueous solution of 0.1 mL 1M AgNO3 in
distilled water was added and irradiated for 60 or 90 s in a
microwave oven (LG Electronics, Korea). At that time, the
color of the PVA solution started to gradually change from
an achromatic color to faint yellow to brownish red at
60 and 90 s of irradiation, respectively, along with a reduc-
tion of Agþ to Ag0. Next, the PVA containing Ag0 solutions
were placed in a plastic syringe and connected through a
metal syringe needle. The solutions were electro-spun
directly using a high voltage power supply (NNC-30 kV-2
mA portable type, Korea). A grounded steel cylinder, 10 cm
away from the tip of the syringe needle, was employed to
collect the nano-fiber mats. The flow rates (mL/h) of the
PVA solutions were controlled using a syringe pump (lure-
lock type, Korea). To resurface Ag NPs on the PVA fibers, a
heat treatment process was conducted at temperatures of
80, 120, and 150
C.
Characterization of PVA nano-fibrous
mat loading Ag NPs
The detailed microstructure of the PVA nano-fiber mats
loading Ag NPs was observed by SEM (SM-65F, JEOL, Japan)
and TEM (JEM2010, JEOL, Japan). Ag NPs were confirmed
by high-resolution transmission electron microscopy
(HRTEM). The average diameter of the electro-spun nano-
fibers was determined by analyzing the SEM images using a
custom code image analysis program.
Absorption spectra of the Ag NPs dispersed in a PVA
solution after microwave irradiation was measured in a
wavelength ranging from 300 to 800 nm using a UV-Vis
spectrophotometer (U2101 PC).
Differential scanning calorimetry (DSC) measurements of
the PVA electro-spun, Ag NPs loaded electrospun PVA mat
before heat treatment (PVA-Ag NPs-1) and Ag NPs loaded
electrospun PVA mat after heat treatment (PVA-Ag NPs-2)
were performed using a DSC (METTLER TOLEDO KOREA-
DSC822e) instrument in the temperature range from 0 to
250
C under a nitrogen atmosphere at a scanning speed of
5
C/min.
X-ray diffractions (Rigaku, D/MAX-2500V) of Agþ loaded
PVA electro-spun and PVA-Ag NPs-2 mats were acquired
226 NGUYEN ET AL.
using Cu Ka radiation. The diffraction angle was ranged
from 5 to 120
2y.
Fourier transform-infrared (FT-IR) spectroscopy analysis
was performed using a Spectrum GX Perkin–Elmer, USA.
The infrared spectra of the PVA electro-spun, PVA-Ag NPs-1,
and PVA Ag NPs-2 were measured over a wavelength range
of 4000–500 cm1.
Mechanical properties
The dimensions of PVA, PVA-Ag NPs-1, and PVA-Ag NPs-2
(wide 1 mm and length 27 mm) were measured using a
digital micrometer and the thickness (100 lm) was mea-
sured by SEM before determining the tensile strength. The
mechanical properties of the sample were determined by
applying tensile test loads to the specimens prepared from
the electro-spun ultra fine nonwoven fiber mats. The meth-
ods used to prepare the specimens for the tensile strength
testing were described in our previous studies.19,20
Antibacterial activities
Cultures of gram-positive bacteria, Staphylococcus aureus
(ATCC No. 6538), and gram-negative bacteria, Escherichia
coli (ATCC No. 8739), were grown and maintained on a
Brain Heart Infusion agar (BHI, Becton-Dicklinson) at 37
C
for 18–24 h prior to the experiments.
Antibacterial tests were then carried out by the disc dif-
fusion method21 using 3.0  106 cfu/mL of Staphylococcus
aureus and 4.0  106 cfu/mL of Escherichia coli. The surface
of the Mueller-Hinton Argar (MHA, Becton-Dickinson) plate
was inoculated with the bacteria strains for testing using a
sterile cotton swab. Next, the samples (1  1 mm2) were
spread onto a MHA plate. After incubation at 37
C for 24 h,
the agar plates were examined for inhibition of bacterial
growth. In these experiments, the PVA mat was used as a
control. The antibacterial activity was evaluated by mea-
suring the zone of inhibition against the test organisms.
RESULTS
Characterization of PVA nano-fibrous
mat loading Ag NPs
Figure 1 shows a SEM micrograph of electrospun PVA mat
loading Ag NPs, which were fabricated under microwave
irradiation for 60 s [Figure 1(a)] (sample A) and 90 s
[Figure 1(b)] (sample B). Sample A consisted of homo-
genous nano-fibrous mats with fiber diameters ranging
between 100 and 200 nm. In contrast, sample B consisted
of nonhomogenous nano-fibrous mats with diameters rang-
ing between 100 and 500. We found that increased micro-
wave irradiation time resulted in an increased fiber dia-
meter because water evaporation increased the polymer
solution concentration at increasing irradiation time.22
Figure 1(c,d) depicts the EDS profiles of large square areas
from samples A and B. As can be seen in these profiles, Ag
as well as O and C elements of PVA were detected. The per-
cent of Ag was determined relative only to C, H, O, and Ag.
The percent of Ag in sample A was 9.93% Ag. This was
higher than the percent Ag in sample B (5.73%).
NANO SILVER LOADED PVA NANO-FIBROUS MATS FOR SKIN APPLICATIONS
 ORIGINAL RESEARCH REPORT

FIGURE 1. SEM micrographs of Ag NPs loaded electro-spun PVA mats with microwave 60 s (a), 90 s (b); (c,d) are EDS profile on the large area
of (a) and (b). [Color figure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

To confirm that Ag NPs were present in the PVA solution
after microwave treatment, UV-Vis absorption spectra of
PVA containing the Ag NPs solution treated with different
microwave irradiation times were obtained (Figure 2). A
maximum absorption located at 416 nm, which is a charac-
teristic peak for Ag NPs, was observed in the PVA/Ag NPs
solution. This peak was shown to be more intense when the
microwave irradiation step was conducted for 90 s than
when conducted for 60 s.
To confirm successful formation of Ag NPs through
microwave irradiation, XRD profiles of AgNO3 loaded elec-
tro-spun PVA with and without microwave-irradiation were
acquired (Figure 3). Typically, the XRD pattern of the PVA
nano-fibrous mat loading Ag NPs had diffraction peaks at a

FIGURE 2. UV-Vis absorption spectra of PVA/Ag solution with differ-

ent microwave irradiation time. [Color figure can be viewed in the FIGURE 3. XRD curves of AgNO3 loaded electrospun PVA mat and Ag
online issue, which is available at wileyonlinelibrary.com.] NPs loaded electrospun PVA mat.

JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | FEB 2011 VOL 96B, ISSUE 2 227
FIGURE 4. SEM micrographs Ag NPs loaded electrospun PVA mats with microwave 60 s at 80
C (a), 120
C (c), and 150
C (e); with 90 s at 150
C
(g); (b,d,f,h) are enlarged image of (a,c,e,h).

2y of 38.2
. This peak could be indexed as (111), which was ers and the intense peaks at 2y ¼ 20.9
; could be indexed
similar to the results reported by Galya et al., who fabri- as 2y ¼ 19.4, 20.9, and 23.6
, which also displayed an XRD
cated a PVA/Ag film for antibacterial applications.23 The profile of both electro spun mats. Similar findings on the
sharp crystalline structure of electro-spun PVA with should- XRD profiles were previously reported.24,25 The peak 2y ¼

228 NGUYEN ET AL. NANO SILVER LOADED PVA NANO-FIBROUS MATS FOR SKIN APPLICATIONS

FIGURE 5. TEM and HRTEM image of Ag NPs loaded electrospun
PVA nano-fiber with 60 s microwave irradiation and heat at 150
C.
9.2 of crystalline PVA-Agþ was high in the XRD profiles of
electro-spun mats that were not microwave-irradiated, while
no peak at 2y ¼ 38.2, which is characteristic of Ag NPs, was
observed. In contrast, a peak at 2y ¼ 38.2 was detected for
electro-spun mats that were microwave-irradiated.26 These
results demonstrate that the addition of Ag and Agþ to PVA
altered the crystalline structure of electro-spun PVA. The Ag
NPs peak was remarkably weak due to the small number of
Ag molecules. This outcome was similar to the results we
obtained in a previous study where we examined PMMA
and Ag substrates.27 The combined results described above
indicate that the Ag NPs were successfully dispersed in PVA
nano-fibers using the microwave and electro-spinning
method.
Electro-spun PVA fibers loading Ag NPs, which were
subjected to microwave irradiation, were placed in an oven
for heat treatment. Electrospun PVA-Ag NPs mats were then
heated for 24 h at the following temperatures: 80, 120, and
150
C. Figure 4(a,c,e) shows the SEM micrographs of sam-
ple A heated at different temperatures while Figure 4(g)
shows a SEM micrograph of sample B heated at 150
C. Fig-
ure 4(b,d,f,h) are three-fold enlarged images of Figure 4
(a,c,e,g) at X90 000. The heat treatment process was found
to affect the morphology of the fiber, as reflected in the
SEM images. For instance, as shown in the comparison
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | FEB 2011 VOL 96B, ISSUE 2
ORIGINAL RESEARCH REPORT
between Figure 4(a,c), under similar experimental condi-
tions (60 s microwave irradiation, 24 h heating), Ag NPs
appeared on the surface of the fiber when the temperature
was changed from 80 to 120
C. Moreover, when the sam-
ples were heat treated at 150
C [Figure 4(e)], the Ag NPs
that were deposited on the surface of the PVA fiber were
larger in size than at treatment at 120
C. Figure 4(g) was
added to compare the effect of microwave-irradiation on
this process. A smaller number of Ag NPs were observed in
Figure 4(g) compared with Figure 4(e), even though the
samples were fabricated under similar conditions with the
only difference being the elimination of microwave-irradia-
tion. The combined results of these experiments suggest
that the most optimal conditions for Ag NP resurfacing
were 60 s of microwave irradiation and heat treatment at
150
C. Variations in the resurfacing process were shown in
more detail in the enlarged images.
Figure 5 shows the TEM and HRTEM images of sample
A heated at 150
C. The TEM images show that Ag NPs
loaded electrospun PVA nano fibers aggregated from a
smaller size (5–15 nm) to a larger size (around 100 nm)
(Figure 5). The Ag NPs were spherically dispersed on the
surface of the fibers. Figure 5(a) shows the resurfacing and
aggregation of Ag NPs on the PVA fiber. Aggregation of Ag
NPs was detected more clearly in the HRTEM image [Figure
5(b)] where the large spherical structures resulted from the
aggregation of smaller Ag NPs (5–10 nm).
To examine the interaction between PVA and Ag, the FT-
IR spectrum of PVA powder, PVA-Ag NPs-1 and PVA-Ag NPs-
2 were acquired (Figure 6). A similar approach was used by
Mbhele et al.28 The main characteristic peaks of PVA were
assigned as follows: skeletal vibrations (814 and 916 cm1);
ACH2Awagging (1376 cm1); and ACAHA and AOAHA
bending (1328 cm1). The peak at 1096 cm1 was attri-
buted to the CAO stretching vibrations of the remaining
nonhydrolyzed vinyl acetate group of PVA.29,30 The peak at
1420 cm1 is the result of the coupling of the OAH in plane
vibration with the CAH wagging vibration.31 The FT-IR
spectrum of PVA-Ag NPs-1 and PVA-Ag NPs-2 are presented
in Figure 6. The decrease in the ratio of 1420 cm1 relative
to the presence of Ag NPs, is indicative of decoupling
between the corresponding vibrations due to interactions
between Ag NPs and the AOH groups of the PVA chains.
This finding was also reported in previous studies.31–33 In
addition, this group reported that the band peaking at 1141
cm1, which occurs due to symmetric CAC stretching, corre-
sponded to the crystalline regions in PVA.31 The peak at
1255 cm1 was determined to be associated with CAOAC
vibrations and indicates cross-linking of some PVA
radicals.34
Thermal characterization of the PVA powder (a), PVA
electro-spun (b), PVA-Ag mats without (c) and with (d) heat
treatment were carried out in the temperature range of 0–
450
C at a heating rate of 5
C per minute in nitrogen. Based
on the thermogram presented in Figure 7, glass transition
temperatures, Tg, (determined by the ASTM midpoint tech-
nique using STARe software) were observed at 75.20 and
73.39
C for PVA powder and the electro-spun PVA mat,
229
FIGURE 6. FT-IR curves of PVA powder, Ag NPs loaded electro-spun
PVA mat before and after heat at 150
C. [Color figure can be viewed
in the online issue, which is available at wileyonlinelibrary.com.]
respectively. Meanwhile, the melting point, Tm, of PVA
and the electro-spun PVA mat were observed at 226.84
and 225.02
C, respectively. In the case of PVA-Ag NPs-1 and
PVA-Ag NPs-2 mats, no Tg were observed, but Tm were
observed at 211.84 and 197.54
C, respectively.
Antibacterial activities
To test the antibacterial activity of the sample, the disc dif-
fusion method was used to assess the activity against S. aur-
eus and E.coli. The inhibition zone was given in Table I. This
test was repeated four times, for each sample. Figure 8
shows the anit-microbial activity of pure PVA, PVA-Ag NPs-
1, PVA-Ag NPs-2 (120
C), and PVA-Ag NPs-2 (150
C)
electro-spun fibrous mats. In these experiments, no zones
of inhibition were observed for pure PVA. As shown in Fig-
ure 8(b,f), (c,g), and (d,h), all Ag NPs loaded electro-spun
PVA fibrous mats displayed a high antibacterial activity
against S. aureus and E.coli. There was a slight increase in
the zones of inhibition when the mat was heated at 120
C,
which was higher than for the mat heated at 150
C. The
zone created by the PVA loading Ag NPs nano-fibrous mat
placed on the bacteria-inoculated surface killed all S. aureus
bacteria under and around the samples. The PVA Ag NPs-2
mat showed the strongest anti-microbial activities against
gram-positive S. aureus and gram-negative E.coli and the
TABLE I. Zone of Inhibition Test from the Disc Diffusion Test
E. coli
Initial Final Inhibition
Dimension Zone Diameter
Sample (mm2) (mm)
Pure PVA mat 1 0
PVA-Ag NPs-1 1 1.5
PVA-Ag NPs-2 (120
C) 1 1.5
PVA-Ag NPs-2 (150
C) 1 1.9
230 NGUYEN ET AL.
FIGURE 7. DSC curves of PVA powder (a), electro-spun PVA (b), Ag
NPs loaded electro-spun PVA 7 before heat treatment (c) and after
heat treatment (d). [Color figure can be viewed in the online issue,
which is available at wileyonlinelibrary.com.]
gram-positive S. aureus was more sensitive then gram-nega-
tive E. coli. As shown in Table I, the PVA-Ag NPs-2 (150
C)
mat produced the highest zone of inhibition against S. aureus
and E.coli. However, the gram-positive bacteria (S. aureus)
was more sensitive than the gram-negative bacteria (E. coli)
on all Ag NPs loaded electrospun PVA mats.
Mechanical properties
Mechanical properties are also important for skin applica-
tions. Therefore, the tensile strength of the electro-spun PVA
mat, PVA-Ag NPs-1 and PVA-Ag NPs-2 (150
C) subjected to
heat treatments at 150
C were also investigated (Figure 9).
The stress–strain curve of the PVA nano-fibrous mat
changed after the introduction of the Ag nano-particles.
Contrary to the pure PVA fibrous mat, where the stress
increased after loading the Ag NPs, the nano-composite
fibrous mats were stronger and more brittle than the pure
PVA fibrous mat. Without heat treatment, the stress
increased from 9 to 35 MPa, whereas with heat treatment,
the stress increased to 47 MPa; however, the strain
decreased from 23 to 15% for both cases. These results cor-
respond to those reported by Mbhele et al.,28 who examined
a PVA-Ag NPs film (59 MPa for 0.73 Wt % Ag) prepared by
the evaporation method using NaBH4 as a reducing agent.
S. aureus
Final Inhibition
Diffusion Zone Diameter Diffusion
(mm) (mm) (mm) n
0 0 0 4
0.5 1.8 0.8 4
0.5 1.9 0.9 4
0.9 2.3 1.3 4
NANO SILVER LOADED PVA NANO-FIBROUS MATS FOR SKIN APPLICATIONS

FIGURE 8. Comparison of the inhibition zone test between (a,e) pure PVA mat; (b,f) PVA-Ag mat; (c,g) PVA-Ag NPs-2 (120
C); (d,h) PVA-Ag NPs-
2 (150
C). The photographs of the disk sensitivity test for E. coli (a–d) and S. aureus (e–h). [Color figure can be viewed in the online issue, which
is available at wileyonlinelibrary.com.]
However, the percentage of Ag in this study was higher
(9.93 Wt % Ag was dispersed into sample A), which caused
a dispersed interruption of Ag NPs on the PVA fibers and
resulted in a more brittle PVA-Ag nano-fibrous composite
mat compared with the PVA mat. The stress–strain curves
indicated that heat treatment had the following effect: after
heat treatment sample A showed increased tensile stress
and brittleness compared with the untreated sample A;
however, the tensile strain was unchanged for both cases
(heat treatment or un-heat treatment). Even though sample
A with and without heat treatment was more brittle than
FIGURE 9. Tensile strength curves of electro-spun PVA, Ag NPs loaded
electro-spun PVA before and after heat treatment. [Color figure can be
viewed in the online issue, which is available at wileyonlinelibrary.
com.]
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH B: APPLIED BIOMATERIALS | FEB 2011 VOL 96B, ISSUE 2
ORIGINAL RESEARCH REPORT
the PVA mat, this sample still holds promise for use in skin
applications because these mats had a higher tensile
strength than mammalian flank skin.35
DISCUSSION
In this study, we used two steps to fabricate PVA-Ag mats
for skin applications. First, the Ag NPs were dispersed on
the electro-spun PVA nano-fibers using microwave and elec-
tro-spinning methods. Then, the Ag NPs were rematerialized
on the surface of the PVA nano-fibers using a heat treatment
process. In the case of loaded Ag NPs, Ag NPs were dis-
persed and stabilized in the PVA solution before electro-
spinning due to the reduction of the alcohol group14 and
the chelating ability of PVA.26,36 Since PVA prevents aggrega-
tion and precipitation of the particles, the Agþ was stabi-
lized by PVA chelation and reduction through microwave-
irradiation.26,36–38 PVA has been frequently used not only as
a particle stabilizer but also as a reductant agent.39 The
reduction of alcohol groups in PVA through microwave-irra-
diation is similar to the reduction of alcohol groups in
PEG.37,38 The reduction during the microwave-irradiation
process was visualized by the naked-eye because the color
of the PVA solution started to gradually change from an ach-
romatic color to a faint yellow to brownish red after 60 and
90 s of irradiation, which was also reported in previous
studies.32 The color of the PVA solution was stable over the
spinning time and the nanoparticles showed almost no
tendency to aggregate because the Ag NPs were capped by
PVA chains. The presence of dispersed Ag NPs in the elec-
tro-spinning solution after microwave-irradiation resulted in
a change in the color of the solution, which was confirmed
by UV-Vis absorption (Figure 2).14,40,41 This suspension was
spun, resulting in the homogeneous dispersion of Ag NPs in
the PVA nano-fibers. Because dispersion of the Ag NPs was
231
homogenous, the surface of the PVA-Ag NPs was smooth in
both cases (Figure 1). However, the EDS profiles indicate
that the PVA nano-fibrous mat contained different amounts
of Ag [Figure 1(c,d)]. Therefore, even though the same
amount of AgNO3 was added, the amount that was loaded
varied (when irradiation time differed). This phenomenon
occurred because of the effect of microwave-irradiation on
the Ag NPs size. Since the microwave-irradiation time was
increased from 60 to 90 s, larger Ag NPs were produced.
The larger Ag NPs were heavy for PVA to carry and possible
to precipitate during microwave and electro-spinning
processes. XRD profiles confirmed that PVA-Ag NPs mats
were successfully produced using microwave irradiation
(Figure 3) whereas the interaction between PVA and Ag
with and without heat treatment was confirmed by FT-IR
(Figure 6) and DSC (Figure 7). The results showed that the
addition of Ag not only affected the structure of the PVA
mat but also changed the crystalline structure and melting
point of the mats.
In this study, the effect of temperature on an Ag NPs
resurfacing process was investigated at the same micro-
wave-irradiation time. The effect of varying the temperature
is shown in Figure 4. When the temperature was increased
(80, 120, and 150
C), the number of Ag NPs on the PVA
surface also increased. Based on the report by Hong et al.,16
we believe this occurred because Ag and Agþ remained in a
cluster while diffusing and then aggregate on the surface of
PVA fibers during heat treatment. Moreover, Luo et al.39
explained that PVA could be cross-linked and their chains
could be cross-linked by Ag and Agþ during hydrothermal
treatment at 160
C. This report also described a potential
mechanism by which Ag could be reduced by PVA and then
aggregate with each other. Through the combined results of
Hong et al. and Luo et al., we can assume that the Ag and
Agþ diffuse from inside the fiber and aggregate on the sur-
face of the PVA fibers and this effect was based on the tem-
perature of the oven. However, by comparing the SEM
images in Figure 4(f,h) [(enlargements of Figure 4(e,g)], we
can see that increasing the microwave-irradiated time from
60 to 90 s did not increase the number of Ag NPs. These
conclusions are based on the EDS profiles. As shown in
Figure 8, the antibacterial activity, as measured by the dia-
meter of the growth inhibition zone, depended on the test
sample used.42 In fact, 60 s of microwave irradiation
followed by heating at 150
C for 24 h was found to be
optimal for preparing the Ag NPs loaded electro-spun PVA
electro-spun mat for the skin because of the large area of
the inhibition zone and high tensile strength.
CONCLUSION
In summary, the PVA-Ag NPs mat, which can be used as a
promoter in wound healing, was fabricated from a sus-
pension of PVA and Ag NPs after microwave-irradiation for
60 s. The PVA-Ag mat was then subjected to heat treatment
at 150
C to resurface the Ag NPs on the surface of the PVA
fibers to increase the antibacterial properties of the mat.
The presence of Ag NPs was confirmed by SEM, TEM, XRD,
EDS, FT-IR, and DSC, verifying that the mat was successfully
232 NGUYEN ET AL.
fabricated using this approach. The fabricated electro-spin-
ning method produced a mat that had a high tensile stress,
which is beneficial for skin applications. The PVA-Ag NPs
mats displayed excellent antimicrobial activity against gram-
positive S. aureus and gram-negative E.coli. Ultimately in
this study, we developed a novel method to fabricate PVA-
Ag NPs mats, which not only possess high tensile stress but
also superb anti-bacterial activities, using a combination of
three simple methods: electrospinning, microwave treat-
ment, and low aging temperature methods.
ACKNOWLEDGMENT
The authors are grateful to Dr. Kap-Ho Lee for his assistance
in performing the experiments outlined in this work.
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