Polymer composites based on poly(vinyl alcohol) filled with silver nanoparticles containing biocompatible
fillers, such as silica and hydroxyapatite, have been prepared and tested for potential antimicrobial application.
An effect of silver content on the properties of prepared polymer composites was evaluated. The
results show that defined bactericidal activity of the elaborated materials was observed silver nanoparticles
concentration of  61 ppm.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3542

Tolstov, A.

SocioEconomic Challenges Journal (Sumy State University)

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  
NANOMATERIALS: APPLICATIONS AND PROPERTIES 
Vol. 2 No 4, 04NABM08(3pp) (2013) 
 
 
2304-1862/2013/2(4)04NABM08(3) 04NABM08-1  2013 Sumy State University 
Preparation of Poly(vinyl alcohol) Based Composites Filled with Biocompatible  
Nanoparticulate Silver Containing Fillers for Highly Efficient Bactericidal Materials 
 
A.L. Tolstov* 
 
Institute of Macromolecular Chemistry of the NAS of Ukraine, 48, Kharkivske Shose, 02160 Kyiv, Ukraine 
 
(Received 20 May 2013; published online 31 August 2013) 
 
Polymer composites based on poly(vinyl alcohol) filled with silver nanoparticles containing biocompati-
ble fillers, such as silica and hydroxyapatite, have been prepared and tested for potential antimicrobial ap-
plication. An effect of silver content on the properties of prepared polymer composites was evaluated. The 
results show that defined bactericidal activity of the elaborated materials was observed silver nanoparti-
cles concentration of  61 ppm. 
 
Keywords: Silver nanoparticles, Polymer, Polymer composites, Films and coatings, Bactericidal activity. 
 
 PACS numbers: 81.05.Qk, 82.35.Np, 87.85.Rs 
 
 
                                               
* tolstov.aleksandr@rambler.ru 
1. INTRODUCTION 
 
Recent development of health care technologies ini-
tiates searching new materials with improved safety 
properties. One group of such materials is antimicrobi-
al polymer composites with highly active antimicrobial 
agents -. There are many types of polymer have been 
used for preparation of such composites, like polyacryl-
ics, vinyl polymers, polyurethanes, polyamides etc. 
However, for faster release an active components into 
environment the highly hydrophilic polymer matrices 
are more preferable.  
In this work we elaborated poly(vinyl alcohol) based 
composites filled with biocompatible fillers, such as 
modified fumed silica and hydroxylapatite, which con-
tain silver nanoparticles and tested for bactericidal 
activity. The structural characteristics and the proper-
ties of prepared polymer composites have been studied 
also.  
 
2. EXPERIMENTAL 
 
2.1 Materials 
 
Poly(vinyl alcohol) (PVC Celvol 103, Мв  1,3-
2,3  104), silver nitrate (AgNO3), fumed silica (SiO2, 
AerosilTM А-300), γ-aminopropyltriethoxysilane (ATS) 
and other chemicals were uses as received.  
 
2.2 Synthesis of Silver Nanoparticles Loaded 
Biocompatible Fillers 
 
Polymer-stabilized silver nanoparticles (AgNP) 
have been prepared in aqueous solution according to 
previously described synthetic approach [1]. 
Hydroxyapatite Ca5(PO4)3(OH) (HAP) has been 
synthesized from Са(СН3СОО)2∙хН2О and Н3РО4 by 
conventional solution deposition technique [2]. To im-
prove an adsorption capacity of SiO2 and as-prepared 
HAP a surface functionalization of the fillers via graft-
ing of ATS layer [3] was carried out by partially modi-
fied approach in aqueous solution at a temperature of 
70-80 °С. Quantitative analysis of NH2 groups content 
shows the follow results: 4.3  10 – 4 and  
1.8  10 – 4 mol/g for SiO2 and HAP, respectively.  
Deposition of AgNP onto a surface of the fillers was 
carried out by mixing aqueous dispersions of fillers and 
AgNP at ambient conditions for appropriate time. This 
approach is allowed to achieve a maximum value of 
AgNP load of 4.1 wt %.  
 
2.3 Preparation of PVA Based Polymer Compo-
sites 
 
For preparation of polymer composites the fillers 
with concentration of AgNP of 2 wt % have been pre-
pared and used. Polymer composites were prepared by 
introducing silver-containing filler into 15 wt % aque-
ous solution of PVA followed by film casting of obtained 
compositions. Concentration of AgNP in composites 
films was varied from 61 to 180 and 760 ppm. Composi-
tion and AgNP content in the samples were identified 
in superscript indexes of the sample code. The samples 
PVAAgNP61, PVAHAP-AgNP61, PVASiO2-AgNP61,  
PVAHAP-AgNP180, PVASiO2-AgNP180, PVAAgNP760 were pre-
pared.  
 
2.4 Characterization 
 
FTIR spectra have been recorded by Bruker 
Tensor® 37 spectrometer in the spectral range of 4000-
400 cm – 1. Morphology of the samples was studied by 
scanning electron microscopy (SEM) via JEOL JSM 
6060 LA equipment at accelerating voltage of 30 kV. 
TGA experiments were performed via TA Q-1500D  
instrument in the temperature range of 20-500 °С.  
Samples for bactericidal testing were prepared by 
dip-coating technique on a glass slides 
(17  17  0.17 mm). Thickness of composite films was 
0.05  0.01 mm. Samples activity was evaluated by 
Escherichia coli DH5α strain (Invitrogen, USA) grown 
on LB-agar at 37 °С for 16 hrs. Comparative bacteri-
cidal efficiency of the composites was tested by measur-
ing a zone of bacteria lysis.  
 
 
 A.L. TOLSTOV PROC. NAP 2, 04NABM08 (2013) 
 
 
04NABM08-2 
3. RESULTS AND DISCUSSION  
 
Functionalization of fillers surfaces and their load-
ing with AgNP were studied by FTIR spectroscopy. 
FTIR spectrum of HAP (Fig. 1) is characterized by 
complex broad stretching vibration bands of “free” and 
H-bonded OH groups in the range of 3500-3100 cm – 1, 
νРО43 – of phosphate ions with maxima at 1095, 1038, 
959, 602 and 564 cm – 1. A presence of intensive bands 
at 1576 and 1425 cm – 1 (νas and νsСОО –, respectively) 
is related to excess of СН3СОО – ions of calcium precur-
sor adsorbed by HAP surface.  
 
 
 
Fig. 1 – FTIR spectra of HAP (1), HAP-APS (2) and HAP-
APS-AgNP (3) 
 
Modification of HAP surface by APS decreases the 
intensities of νOH and increases the intensities of νCH 
bands in the range of 3000-2800 cm – 1 due to their inter-
action of the filler with APS modifier. An appearance of 
– NH2 groups on a filler surface is not clearly identified 
by FTIR analysis because of overlapping νNH and γNH 
with νОН and νРО43 – bands, correspondingly. Adsorp-
tion of AgNP has minor effect on spectral characteristics 
of HAP due to relatively low AgNP content. 
In the FTIR spectrum of SiO2 (Fig. 2) a broad νOH 
band of surface hydroxyls at 3700-3200 cm – 1, νОН of 
Н2О molecules with maximum at 1630 cm – 1, complex 
absorbance band of Si-O-Si groups in the range of 1300-
950 cm – 1 with maxima at ~ 1200 and ~ 1097 cm – 1, as 
well as stretching vibrations band of О-Si-O fragments 
at 810 cm – 1 have been identified.  
 
 
 
Fig. 2 – FTIR spectra of SiO2 (1), SiO2-APS (2) and SiO2-APS-
AgNP (3) 
Functionalization of SiO2 by APS leads to decreas-
ing intensities of νОН band of hydroxyl groups on SiO2 
surface and appearance of νСН and weak γС-N bands 
at 3000-2800 and 1414 cm – 1. Due to relatively low lev-
el of AgNP adsorption on SiO2 surface there are no 
changes in the FTIR spectrum of silver-containing filler 
was found also.  
When the AgNP loaded filler was introduced into 
hydrophilic PVA matrix the morphology analysis of 
obtained composites was carried out by SEM. It was 
found that PVASiO2-AgNP180 sample (Fig. 3a) is character-
ized by uniform distribution of the nanosized filler 
(AgNP loaded SiO2) in polymer matrix and absence of 
large aggregates (≥ 1 m) of the particles. Otherwise, 
PVAHAP-AgNP180 composite (Fig. 3a) have clearly  
heterogeneous structure due to filler peculiarities (HAP 
consist of the particles with a size of 1-8 m).  
 
 
 
 
 
Fig. 3 – SEM photographs of PVASiO2-AgNP180 (a) and  
PVAHAP-AgNP180 (b) composites 
 
Comparative analysis of thermal properties of pure 
PVA and PVA in the presence of AgNP was performed 
using TGA technique. The temperatures of onset and 
maxima as well as weight loss at each stage of termoox-
idative destruction (Tonset, Tmax and Δm, respectively) 
were found and analyzed.  
Typical PVA is characterized by multistage degrada-
tion behavior: 1-st stage at 70-160 °С (desorption of H2O 
and beginning of dehydratation process); 2-nd stage at 240-
280 °С (dehydratation of PVA macrochain and formation 
of poly-ene structures); 3-rd stage at 320-410 °С (Diels-
Alder condensation of poly-ene fragments that leads to 
formation of aliphatic, cycloaliphatic and aromatic struc-
tures in the matrix); and 4-th stage at 420-480 °С (for-
mation of charcoal with high aromatics content).  
a 
c 
v, cm – 1 
v, cm – 1 
A
, 
a
r
b
. 
u
n
it
 
A
, 
a
r
b
. 
u
n
it
 
 PREPARATION OF POLY (VINYL ALCOHOL)… PROC. NAP 2, 04NABM08 (2013) 
 
 
04NABM08-3 
Presence of AgNP in PVA changes the thermooxida-
tive behavior of polymer matrix. It was found that nar-
rowing the temperature intervals of basic stages of 
thermooxidative destruction and shift of Tonset to low 
temperatures by 10-40 °С, as well as an appearance of 
new degradation stages at 170-210 °C and 280-310 °C 
is probably due to catalytic effect of AgNP on termode-
struction of PVA matrix (catalytic properties of AgNP 
on different chemical reactions are well known and 
applied in organic synthesis [4, 5]). Moreover, AgNP 
reduces a weight loss rate of PVA in some degradation 
stages probably due to inclusion some volatile products 
of PVA degradation in catalytic reactions with matrix 
macrochains. 
The results of antimicrobial tests of prepared com-
posites are presented in Table 1.  
 
Table 1 – Antimicrobial properties of PVA based composites 
 
No Sample AgNP content, 
ppm 
Zone of bacte-
ria lysis, mm 
1 PVA 0 0 
2 PVAAgNP61 61  0.2 
3 PVAHAP-AgNP61 61 0.5-0.7 
4 PVASiO2-AgNP61 61 0.5-1.0 
5 PVAHAP-AgNP180 180 2.0-2.5 
6 PVASiO2-AgNP180 180 2.5-2.8 
7 PVAAgNP760 760 3.0-4.0 
 
The pure PVA and PVA with 61 ppm of AgNP 
(PVAAgNP61) have no bactericidal effect in selected test 
conditions. However, the HAP or SiO2 filled composites 
with 61 ppm of AgNP content (PVAHAP-AgNP61 and PVA-
SiO2-AgNP61) are characterized by zone of bacteria lysis of 
0.7-1.0 mm. A difference in bactericidal activity of un-
filled and filler-containing composites with 61 ppm of 
AgNP content could be interpreted as filler-induced 
ionization of AgNP on a fillers’ surface which possess 
improved diffusion of bactericidal agent (Ag+) to the 
environment.  
High antibacterial activity (zone of bacteria lysis 
reaches 2.8 mm) was found for PVA-based filled compo-
site films with 180 ppm of AgNP content. A slightly 
lower bactericidal activity of PVAHAP-AgNP180 compared 
to PVASiO2-AgNP180 sample is due to larger HAP particle 
size that not allowed to provide uniform diffusion of 
Ag+ from a bulk and a surface of composite films to 
environment. A direct correlation between bactericidal 
activity of the composites and AgNP content was de-
tected from experimental results.  
Thus the proposed approach is allowed to produce 
efficient bactericidal polymer composites based on hy-
drophilic poly(vinyl alcohol). Using silver nanoparticles 
loaded biocompatible fillers, like hydroxyapatite and 
nanosilica, was found to be perspective to possess high 
bactericidal activity of obtained materials. Surface 
functionalization of fillers improves its adsorption ca-
pacity to nanoparticulate silver. Polymer composites, 
which contain AgNP loaded filler, have stronger bacte-
ricidal effect in comparison with AgNP containing PVA 
without filler at the same concentration of silver nano-
particles.  
 
REFERENCES 
 
1. Z. Zhang, M. Han, J. Mater. Chem. 13, 641 (2003). 
2. S.-C. Liou, S.-Y. Chen, H.-Y. Lee, J.-S. Bow, Biomaterials 
25, 189 (2004). 
3. A.R. Morrill, D.T. Duong, S.J. Lee, M. Moskovits, Chem. 
Phys. Lett. 473, 116 (2009).  
4. V. Raji, M. Chakraborty, P.A. Parikh, Ind. Eng. Chem. 
Res. 51, 5691 (2012).  
5. H. Cong, C.F. Becker, S.J. Elliott, M.W. Grinstaff, 
J.A. Porco, J. Am. Chem. Soc. 132, 7514 (2010). 
 


English

Preparation of Poly(vinyl alcohol) Based Composites Filled with Biocompatible Nanoparticulate Silver Containing Fillers for Highly Efficient Bactericidal Materials

Electronic Sumy State University Institutional Repository

PROCEEDINGS OF THE INTERNATIONAL CONFERENCE  NANOMATERIALS: APPLICATIONS AND PROPERTIES Vol. 2 No 4, 04NABM08(3pp) (2013)   2304-1862/2013/2(4)04NABM08(3) 04NABM08-1  2013 Sumy State University Preparation of Poly(vinyl alcohol) Based Composites Filled with Biocompatible  Nanoparticulate Silver Containing Fillers for Highly Efficient Bactericidal Materials  A.L. Tolstov*  Institute of Macromolecular Chemistry of the NAS of Ukraine, 48, Kharkivske Shose, 02160 Kyiv, Ukraine  (Received 20 May 2013; published online 31 August 2013)  Polymer composites based on poly(vinyl alcohol) filled with silver nanoparticles containing biocompati-ble fillers, such as silica and hydroxyapatite, have been prepared and tested for potential antimicrobial ap-plication. An effect of silver content on the properties of prepared polymer composites was evaluated. The results show that defined bactericidal activity of the elaborated materials was observed silver nanoparti-cles concentration of  61 ppm.  Keywords: Silver nanoparticles, Polymer, Polymer composites, Films and coatings, Bactericidal activity.   PACS numbers: 81.05.Qk, 82.35.Np, 87.85.Rs                                                  * tolstov.aleksandr@rambler.ru 1. INTRODUCTION  Recent development of health care technologies ini-tiates searching new materials with improved safety properties. One group of such materials is antimicrobi-al polymer composites with highly active antimicrobial agents -. There are many types of polymer have been used for preparation of such composites, like polyacryl-ics, vinyl polymers, polyurethanes, polyamides etc. However, for faster release an active components into environment the highly hydrophilic polymer matrices are more preferable.  In this work we elaborated poly(vinyl alcohol) based composites filled with biocompatible fillers, such as modified fumed silica and hydroxylapatite, which con-tain silver nanoparticles and tested for bactericidal activity. The structural characteristics and the proper-ties of prepared polymer composites have been studied also.   2. EXPERIMENTAL  2.1 Materials  Poly(vinyl alcohol) (PVC Celvol 103, Мв  1,3-2,3  104), silver nitrate (AgNO3), fumed silica (SiO2, AerosilTM А-300), γ-aminopropyltriethoxysilane (ATS) and other chemicals were uses as received.   2.2 Synthesis of Silver Nanoparticles Loaded Biocompatible Fillers  Polymer-stabilized silver nanoparticles (AgNP) have been prepared in aqueous solution according to previously described synthetic approach [1]. Hydroxyapatite Ca5(PO4)3(OH) (HAP) has been synthesized from Са(СН3СОО)2∙хН2О and Н3РО4 by conventional solution deposition technique [2]. To im-prove an adsorption capacity of SiO2 and as-prepared HAP a surface functionalization of the fillers via graft-ing of ATS layer [3] was carried out by partially modi-fied approach in aqueous solution at a temperature of 70-80 °С. Quantitative analysis of NH2 groups content shows the follow results: 4.3  10 – 4 and  1.8  10 – 4 mol/g for SiO2 and HAP, respectively.  Deposition of AgNP onto a surface of the fillers was carried out by mixing aqueous dispersions of fillers and AgNP at ambient conditions for appropriate time. This approach is allowed to achieve a maximum value of AgNP load of 4.1 wt %.   2.3 Preparation of PVA Based Polymer Compo-sites  For preparation of polymer composites the fillers with concentration of AgNP of 2 wt % have been pre-pared and used. Polymer composites were prepared by introducing silver-containing filler into 15 wt % aque-ous solution of PVA followed by film casting of obtained compositions. Concentration of AgNP in composites films was varied from 61 to 180 and 760 ppm. Composi-tion and AgNP content in the samples were identified in superscript indexes of the sample code. The samples PVAAgNP61, PVAHAP-AgNP61, PVASiO2-AgNP61,  PVAHAP-AgNP180, PVASiO2-AgNP180, PVAAgNP760 were pre-pared.   2.4 Characterization  FTIR spectra have been recorded by Bruker Tensor® 37 spectrometer in the spectral range of 4000-400 cm – 1. Morphology of the samples was studied by scanning electron microscopy (SEM) via JEOL JSM 6060 LA equipment at accelerating voltage of 30 kV. TGA experiments were performed via TA Q-1500D  instrument in the temperature range of 20-500 °С.  Samples for bactericidal testing were prepared by dip-coating technique on a glass slides (17  17  0.17 mm). Thickness of composite films was 0.05  0.01 mm. Samples activity was evaluated by Escherichia coli DH5α strain (Invitrogen, USA) grown on LB-agar at 37 °С for 16 hrs. Comparative bacteri-cidal efficiency of the composites was tested by measur-ing a zone of bacteria lysis.     A.L. TOLSTOV PROC. NAP 2, 04NABM08 (2013)   04NABM08-2 3. RESULTS AND DISCUSSION   Functionalization of fillers surfaces and their load-ing with AgNP were studied by FTIR spectroscopy. FTIR spectrum of HAP (Fig. 1) is characterized by complex broad stretching vibration bands of “free” and H-bonded OH groups in the range of 3500-3100 cm – 1, νРО43 – of phosphate ions with maxima at 1095, 1038, 959, 602 and 564 cm – 1. A presence of intensive bands at 1576 and 1425 cm – 1 (νas and νsСОО –, respectively) is related to excess of СН3СОО – ions of calcium precur-sor adsorbed by HAP surface.     Fig. 1 – FTIR spectra of HAP (1), HAP-APS (2) and HAP-APS-AgNP (3)  Modification of HAP surface by APS decreases the intensities of νOH and increases the intensities of νCH bands in the range of 3000-2800 cm – 1 due to their inter-action of the filler with APS modifier. An appearance of – NH2 groups on a filler surface is not clearly identified by FTIR analysis because of overlapping νNH and γNH with νОН and νРО43 – bands, correspondingly. Adsorp-tion of AgNP has minor effect on spectral characteristics of HAP due to relatively low AgNP content. In the FTIR spectrum of SiO2 (Fig. 2) a broad νOH band of surface hydroxyls at 3700-3200 cm – 1, νОН of Н2О molecules with maximum at 1630 cm – 1, complex absorbance band of Si-O-Si groups in the range of 1300-950 cm – 1 with maxima at ~ 1200 and ~ 1097 cm – 1, as well as stretching vibrations band of О-Si-O fragments at 810 cm – 1 have been identified.     Fig. 2 – FTIR spectra of SiO2 (1), SiO2-APS (2) and SiO2-APS-AgNP (3) Functionalization of SiO2 by APS leads to decreas-ing intensities of νОН band of hydroxyl groups on SiO2 surface and appearance of νСН and weak γС-N bands at 3000-2800 and 1414 cm – 1. Due to relatively low lev-el of AgNP adsorption on SiO2 surface there are no changes in the FTIR spectrum of silver-containing filler was found also.  When the AgNP loaded filler was introduced into hydrophilic PVA matrix the morphology analysis of obtained composites was carried out by SEM. It was found that PVASiO2-AgNP180 sample (Fig. 3a) is character-ized by uniform distribution of the nanosized filler (AgNP loaded SiO2) in polymer matrix and absence of large aggregates (≥ 1 m) of the particles. Otherwise, PVAHAP-AgNP180 composite (Fig. 3a) have clearly  heterogeneous structure due to filler peculiarities (HAP consist of the particles with a size of 1-8 m).       Fig. 3 – SEM photographs of PVASiO2-AgNP180 (a) and  PVAHAP-AgNP180 (b) composites  Comparative analysis of thermal properties of pure PVA and PVA in the presence of AgNP was performed using TGA technique. The temperatures of onset and maxima as well as weight loss at each stage of termoox-idative destruction (Tonset, Tmax and Δm, respectively) were found and analyzed.  Typical PVA is characterized by multistage degrada-tion behavior: 1-st stage at 70-160 °С (desorption of H2O and beginning of dehydratation process); 2-nd stage at 240-280 °С (dehydratation of PVA macrochain and formation of poly-ene structures); 3-rd stage at 320-410 °С (Diels-Alder condensation of poly-ene fragments that leads to formation of aliphatic, cycloaliphatic and aromatic struc-tures in the matrix); and 4-th stage at 420-480 °С (for-mation of charcoal with high aromatics content).  a c v, cm – 1 v, cm – 1 A, arb. unit A, arb. unit  PREPARATION OF POLY (VINYL ALCOHOL)… PROC. NAP 2, 04NABM08 (2013)   04NABM08-3 Presence of AgNP in PVA changes the thermooxida-tive behavior of polymer matrix. It was found that nar-rowing the temperature intervals of basic stages of thermooxidative destruction and shift of Tonset to low temperatures by 10-40 °С, as well as an appearance of new degradation stages at 170-210 °C and 280-310 °C is probably due to catalytic effect of AgNP on termode-struction of PVA matrix (catalytic properties of AgNP on different chemical reactions are well known and applied in organic synthesis [4, 5]). Moreover, AgNP reduces a weight loss rate of PVA in some degradation stages probably due to inclusion some volatile products of PVA degradation in catalytic reactions with matrix macrochains. The results of antimicrobial tests of prepared com-posites are presented in Table 1.   Table 1 – Antimicrobial properties of PVA based composites  No Sample AgNP content, ppm Zone of bacte-ria lysis, mm 1 PVA 0 0 2 PVAAgNP61 61  0.2 3 PVAHAP-AgNP61 61 0.5-0.7 4 PVASiO2-AgNP61 61 0.5-1.0 5 PVAHAP-AgNP180 180 2.0-2.5 6 PVASiO2-AgNP180 180 2.5-2.8 7 PVAAgNP760 760 3.0-4.0  The pure PVA and PVA with 61 ppm of AgNP (PVAAgNP61) have no bactericidal effect in selected test conditions. However, the HAP or SiO2 filled composites with 61 ppm of AgNP content (PVAHAP-AgNP61 and PVA-SiO2-AgNP61) are characterized by zone of bacteria lysis of 0.7-1.0 mm. A difference in bactericidal activity of un-filled and filler-containing composites with 61 ppm of AgNP content could be interpreted as filler-induced ionization of AgNP on a fillers’ surface which possess improved diffusion of bactericidal agent (Ag+) to the environment.  High antibacterial activity (zone of bacteria lysis reaches 2.8 mm) was found for PVA-based filled compo-site films with 180 ppm of AgNP content. A slightly lower bactericidal activity of PVAHAP-AgNP180 compared to PVASiO2-AgNP180 sample is due to larger HAP particle size that not allowed to provide uniform diffusion of Ag+ from a bulk and a surface of composite films to environment. A direct correlation between bactericidal activity of the composites and AgNP content was de-tected from experimental results.  Thus the proposed approach is allowed to produce efficient bactericidal polymer composites based on hy-drophilic poly(vinyl alcohol). Using silver nanoparticles loaded biocompatible fillers, like hydroxyapatite and nanosilica, was found to be perspective to possess high bactericidal activity of obtained materials. Surface functionalization of fillers improves its adsorption ca-pacity to nanoparticulate silver. Polymer composites, which contain AgNP loaded filler, have stronger bacte-ricidal effect in comparison with AgNP containing PVA without filler at the same concentration of silver nano-particles.   REFERENCES  1. Z. Zhang, M. Han, J. Mater. Chem. 13, 641 (2003). 2. S.-C. Liou, S.-Y. Chen, H.-Y. Lee, J.-S. Bow, Biomaterials 25, 189 (2004). 3. A.R. Morrill, D.T. Duong, S.J. Lee, M. Moskovits, Chem. Phys. Lett. 473, 116 (2009).  4. V. Raji, M. Chakraborty, P.A. Parikh, Ind. Eng. Chem. Res. 51, 5691 (2012).  5. H. Cong, C.F. Becker, S.J. Elliott, M.W. Grinstaff, J.A. Porco, J. Am. Chem. Soc. 132, 7514 (2010).  

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Preparation of Poly(vinyl alcohol) Based Composites Filled with Biocompatible Nanoparticulate Silver Containing Fillers for Highly Efficient Bactericidal Materials

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