2010 WASE International Conference on Information Engineering
Synthesis of Composite Antibacterial Agent by Chemical Method
Huifang Yang Shuxia Ren
School of material science School of material science
and engineering and engineering
Shijiazhuang TieDao Shijiazhuang TieDao
University University
Shiajizhuang, 050043, Shiajizhuang, 050043,
China China
yhf989@sina.com ren-shu-xia@163.com
Abstract—the composite antibacterial agents were
prepared with nano-hydroxyapatite containing polyvinyl
alcohol, copper ions and zinc ions via the parcels and ion
exchange respectively. The as-prepared antibacterial
agents were characterized by X-ray diffraction, infrared
spectrogram and scanning electron microscopy. The
results show that PVA has been wrapped in the surface
of hydroxyapatite, and copper and zinc ions had entered
the structure of hydroxyapatite. The diameters of the
antibacterial ring of Escherichia coli, Candida albicans,
Bacillus subtilis and Staphylococcus aureus could be up
to 18.32 mm, 14.09mm, 16.17mm and 21.05 mm
respectively, which reveal that the composites possess
excellent and a broad-spectrum antibacterial property.
Keywords composites antibacterial agent, polyvinyl
alcohol, antibacterial property, mechanism
I. INTRODUCTION
Harmful bacteria exist anywhere in the world such as air,
water, soil, surfaces of objects and our skins, etc. They have
threatened the health of human beings seriously. For this
reason, all increasing attention has been paid to restraining
and killing the harmful bacteria, and to building a healthy
environment, so the antibacterial materials have been
developed as ecological functional materials, and become
one of the hot topics in the fields of functional materials
research [1-3]. Antibacterial agents can be divided into two
types: inorganic and organic biological [4]. Inorganic
antibacterial materials, especially doping silver ion, have
many advanced functions and features ， including high
stability ， strong antibacterial function ， high safety and
heat-resistant property [5-6], but it results in high cost and
color-changed easily [7-8]. While organic antimicrobial agents
have instantaneous antibacterial property, they cannot be
used at high temperature [9]. Therefore it is necessary to
prepare one type composites antimicrobial agent with the
advantages of the above mentioned agent by composing
them together. Successful development of the preparation of
composites antimicrobial agent should bring a revolution to
the field of antimicrobial agents.
In this study, the composite antimicrobial agents were
prepared using nano-hydroxyapatite as a carrier and
978-0-7695-4080-1/10 $26.00 © 2010 IEEE
DOI 10.1109/ICIE.2010.29
Jia Hou Li Zhifang
School of material science School of material science
and engineering and engineering
Shijiazhuang TieDao Shijiazhuang TieDao
University University
Shiajizhuang, 050043, Shiajizhuang, 050043,
China China
Houjia8480@126.com zf-l2007@163.com
polyvinyl alcohol (PVA), copper and zinc ions as
antimicrobial components by parceling and ion exchanging.
The antimicrobial activities of antimicrobial agents were
tested by the size of inhibition zone diameters, and the
microstructures of the agents were characterized by XRD,
SEM and IR.
II. EXPERIMENTAL
A. Preparation of Composites Antibacterial Agents
Nano-hydroxyapatite powders were synthesized by the
homogeneous precipitation method. After the powders were
heated 12 hours in the three-necked flask, PVA was put into
them with reacting 1~2 hours at 90 ℃. Then copper and zinc
ions were brought into the above composites product with
aging 24 hours and ultrasonic oscillator for 30 min at 60℃.
After filtered, cleaned and dried 1 hours at 120 ℃ , the
organic/inorganic composite antimicrobial agents were
gained.
B. Characterization of Composites Antibacterial Agents
The antibacterial property the as-prepared agents were
evaluated by measuring the diameter of Antibacterial ring [10]
of Escherichia coli, Candida albicans, Bacillus subtilis and
Staphylococcus aureus respectively.The as-prepared agents
were characterized by X-ray diffraction (XRD, X ＇ Pert
MPD) with Cu kα radiation (λ=0.15418μm), and scanning
electron microscopy (SEM: Type JSM-5610LV) with an
accelerating voltage of 20kV, and infrared spectroscopy (IR:
60SXB) ．
III. RESULTS AND DISCUSSIONS
A. The antibacterial property of polyvinyl alcohol
/hydroxyapatite composite hydrogel
The results of antibacterial property of polyvinyl alcohol
/hydroxyapatite composite hydrogel were listed in table 1.
The samples of number 1, 2, 3 and 4 in the table 1 are
composite hydrogel in which amount of polyvinyl alcohol
were 0%, 1.4%, 2.1% and 2.8% respectively. d1, d2, d3 and d4
were the bacteriostatic ring diameter of Escherichia coli,
Candida albicans, Bacillus subtilis and Staphylococcus
aureus respectively. According to the table1, it can be seen
that nano-hydroxyapatite alone has little effect on the four
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bacteria. After it compounded with polyvinyl alcohol C. X-ray diffraction (XRD) analysis
forming the composite hydrogel, which all have better Fig.2 and Fig.3 show XRD patterns of the pure
antibacterial property on Staphylococcus aureus, Bacillus hydroxyapatite and the composite antibacterial agent
subtilis and Candida albicans. But it is a pity that composite respectively. Comparing the two figures, it can be seen that
hydrogel has no effect on Escherichia coli. So the following the main diffraction peaks , 2, 31.8° (300) and 25.9° (002) ,
experiments mainly study on the antibacterial property of of the antibacterial agent were the same as the pure
Escherichia coli. hydroxyapatite, which indicates Nano-hydroxyapatite of the
TABLE I. THE BACTERIOSTATIC RING DIAMETER OF COMPOSITE
agent keeps the existing composition of hexagonal lattice
HYDROGEL after being compounded, but peak widths of the former were
wider than those of latter. Because of the parallel channel of
Escherichia Candida Bacillus Staphyloco
coli albicans subtilis ccus aureus
c shaft in the microstructure of hydroxyapatite [11], it is easy
No.
to absorb metal ions like silver ions, copper ions and zinc
d4/mm d2/mm d3/mm d1/mm
ions, etc, forming more complex composition. Cu2+ and Zn2+
1 6 < d3<7 6 < d2 <7 6 < d3<7 6 < d1 < 7 are not only absorbed on crystallization of hydroxyapatite,
2 6 .50 15.12 15.02 14.00 but also they can substitute for Ca2+ and come into the lattice
structure of hydroxyapatite. The reason is that the
3 6 .40 11.13 20.00 15.00 crystallographic radius of copper ions and zinc ions are
4 6.70 14.01 15.01 20.00 0.72Å and 0.74Å separately, which are smaller than 0.99Å of
calcium ions. Comparing nano-hydroxyapatite, the lattice
constant of composite products turns smaller maybe that
B. The antibacterial property of the composite hydrogel Cu2+, Zn2+ substitute for Ca2+ and make grain size smaller.
with metal ions. That is in concordance with the wider of the peak width of
Based on the above results, 2.8% of polyvinyl alcohol is XRD and the smaller grain size in the SEM photograph.
chosen to prepare composite antibacterial with metal ions.
Firstly, the antibacterial property of the composite
antibacterial agent parepared with copper ion and zinc ion 4000

respactively were determined. The results were listed in

Fig.1, which shows that when the amount of copper ion and 3000
Intensity/cps

zinc ion were 10%and 15% respectively, the corresponding

composite agents had the best antibacterial property. 2000
Then the composite antibacterial agent was prepared by
adding 10% copper ion and 15%zinc ion together to
composite hydrogel with 2.8% polyvinyl alcohol. The 1000

antibacterial testing results of this product shows the

diameter of the antibiotic zone for Escherichia coli, Candida 0
20 30 40 50 60
albicans , Bacillus subtilis and Staphylococcus aureus were 2θ /degree
up to 18.32 mm, 14.09mm, 16.17mm and 21.05mm
respectively . It concluded that the product has excellent Figue 2 XRD pattern of the hydroxyapatite
antibacterial property not only for Candida albicans, Bacillus
subtilis and Staphylococcus aureus but also for Escherichia
2.

coli, and was a broad-spectrum antibacterial agent. 4000

37

3000
Intensity/cps

3.4

2+
9 CU
the inhibition zone diameter/mm

2+
ZN
2000

8
37
31

1.8
2.6

43
908

1.9
4

20
3.1
3.0

1000
80

1.7
2.9

66
2.2

7
67
2.0

0
6 20 30 40 50 60
2θ /degree
5 Figue3 XRD pattern of the composite
antimicrobial agent
0 3 5 8 10 13 15 18 20
the quanlity ofcopper ions and zinc ions/%
D. The analysis of infrared spectrogram (IR)
Figure 1. The effects of metal ions on antibacterial property of the
composite antibacterial agents Fig.4 shows the infrared spectrogram of composite
antibacterial agent. The stretching vibration peaks of -OH, C-
H, C-O of PVA is 3430 cm-1, 854 cm-1and 1095 cm-1

90
separately, and its zonal absorption peak is 1144 cm-1. In In a word, the antibacterial mechanism of composite
fig.4, stretching vibration peaks of -OH in compound antibacterial agents is that metal ions escape and make the
products move low wave value (3430 ~3381 cm-1), which deactivation of enzyme in bacteria and much of associated
maybe because hydroxyl is easy to associate hydrogen, with hydroxyl in polyvinyl alcohol / nano- hydroxyapatite
the increase of associated degree, absorption peaks move low contracts cell membraue erodes enzyme of cell membraue
wave value and peak widths are wider. There is plenty of and changes the property of protein.
free hydroxyl in nano-hydroxyapatite and polyvinyl alcohol,
when there is associated hydroxyl in existence too, this effect
is obvious that illustrates there is the interaction between
hydroxyl in nano-hydroxyapatite and hydroxyl of polyvinyl
alcohol. The peak point at 1095 cm-1 is wider that is because
of the existence of C-O stretching vibration peak, the
superposition of two peak values turns the peak wider. The
disappearance of the zonal absorption peak at 1144 cm-1
also illustrates that the preparation affects the structure of
PVA. Hydroxyl of PVA and Ca2+ in hydroxyapatite can form
a coordination structure reported[12], there is the interaction
Figue.5 the SEM images of nano-hydroxyapatite
between them that can let stretching vibration peaks of
hydroxyl in PVA move low wave value. The interaction
between them also shows that nano-hydroxyapatite and PVA
are not simple physical blending. The main reason may be
that hydroxyl of PVA and Ca2+ in hydroxyapatite have the
effect with each other, which make the stronger
intermolecular composite structure substitute for the effect of
intermolecular hydrogen bonds in PVA.
4.5 4. 5

4.0 4. 0

3. 5

Figue.6 the SEM image of composite antimicrobial agent

3.0 3. 0

2. 5 V. CONCLUSIONS
T%
%T

2.0 2. 0
The composite antibacterial agents gain antibacterial
1. 5 activity of broad-spectrum. The inhibition zone diameters of
1.0 1. 0
Escherichia coli, Staphylococcus aureus, Candida albicans
and Bacillus subtilis could be up to 18.32 mm, 14.09mm,
16.17mm and 21.05 mm.The wider of the peak width of
0. 5

0.0 0. 0
4000
4000 3000
3000
2000
2000
100
1000
1000
XRD and the smaller grain size in the SEM photograph
result from Cu2+, Zn2+ substituting for Ca2+ in the composite
cm- 1

cm -1 0
Figue.4 Infrared spectroscopy of composite
antimicrobial agent
E. Scanning electron microscope (SEM)
Fig.5 and Fig.6 show the SEM photographs of nano-
hydroxyapatite and composite antibacterial agent
respectively. From the figures, the particle size in the SEM
images of composite antibacterial agent is obviously smaller
than that of nano-hydroxyapatite. That is in concordance
with the result of XRD analysis.
IV. THE ANTIBACTERIAL MECHANISM ANALYSIS
The antibacterial mechanism of composite antibacterial
agents can divide into two parts, one is the antibacterial
synergistic effect between organic and hydroxyapatite kills
Staphylococcus aureus, Candida albicans and Bacillus
subtilis, the other one is the antibacterial synergistic effect
between copper ions and zinc ions kill Escherichia coli,
which makes up for the deficiency of polyvinyl alcohol /
hydroxyapatite which fail resisting Escherichia coli.
antibacterial agent. The result of IR shows that hydroxyl of
PVA and Ca2+ in hydroxyapatite have the effect with each
other, which make the stronger intermolecular composite
structure substitute for the effect of intermolecular hydrogen
bonds in PVA.and that also shows nano-hydroxyapatite and
PVA are not simple physical blending.
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