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J. Phys. Chem.

C 2007, 111, 3629-3635


Synthesis and Characterization of Antibacterial Ag-SiO2 Nanocomposite

Young Hwan Kim, Don Keun Lee, Hyun Gil Cha, Chang Woo Kim, and Young Soo Kang*,
Department of Chemistry, Pukyong National UniVersity, Busan 608-737, Korea, and Department of Chemistry and Chemical Biology, HarVard UniVersity, Cambridge, Massachusetts 02138 ReceiVed: December 4, 2006; In Final Form: January 4, 2007

In order to increase antibacterial abilities and avoid aggregation of Ag nanoparticles, Ag-SiO2 nanocomposites were studied to achieve hybrid structure. SiO2 nanoparticles synthesized by the Stober method served as seeds for immobilization of Ag. The chemical binding structure and morphology of Ag-SiO2 nanocomposites and SiO2 nanoparticles were investigated with X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The antibacterial properties of Ag-SiO2 nanocomposites were examined with disk diffusion assay and minimum inhibitory concentration (MIC). Results showed that Ag nanoparticles are homogeneously formed on the surface of SiO2 nanoparticles without aggregation and showed excellent antibacterial abilities.

Introduction The synthesis of nanosized particles is a growing research field in chemical science, in accordance with the extensive development of nanotechnology.1-3 The size-induced properties of nanoparticles enable the development of new applications or the addition of flexibility to existing systems in many areas, such as catalysis, optics, microelectronics, and so on.4-7 Monoand bimetallic particles in the nanosize regime find extensive applications in catalysis, since with reduced size, increased surface area increases catalytic activity.8 Various routes are available for the synthesis of metal nanoparticles. These methods are based on the reduction process of precursor metal ions that includes chemical reduction using different reducing agents, photoreduction, sonochemical, radiolytic methods, etc.9-15 Ag nanoparticles have attracted considerable attention because of their catalytic, optical, and conducting properties.1,16,17 The advantages of inorganic antibacterial materials are superior to those of organic antibacterial materials in durability, heat resistant, toxicity, selectivity, and so on. The usefulness of Ag as an antibacterial agent has been known for a long time. It is an effective agent with low toxicity, which is especially important in topical antibacterial treatment.18 Its synthesis has been achieved via various routes, including microemulsion technique, sonochemical reduction, photochemical technique, etc.11,19-21 These synthetic methods are time-consuming and require expensive instruments. Also, Ag nanoparticles synthesized by these methods are easily aggregated,which causes deterioration of their chemical properties and decreases their antibacterial properties. To improve these problems and to increase antibacterial properties, we synthesized Ag nanoparticles formed on the surface of SiO2 nanoparticles. If Ag is formed on supporting materials, the release time of Ag can be delayed for a long time so that Ag-supported materials will have great potential for antibacterial applications.22-27 At present, many antibacterial agents have been mainly based on organic
* Address correspondence to this author: tel + 82 51 620 6379; fax + 82 51 628 8147; e-mail Pukyong National University. Harvard University.

TABLE 1: Experimental Details of Ag-SiO2 Nanocomposite Series

reactant material Ag-SiO2-1 Ag-SiO2-2 Ag-SiO2-3 Ag-SiO2-4 SiO2 (mmol) 50 50 50 50 H2O (mL) 200 200 200 200 AgNO3 (mmol) 8.83 26.49 8.83 26.49 NH3 (mmol) pH 9.66 9.62 10.75 10.79

105.28 105.28

materials, which are often not usable under conditions where chemical durability is required.28,29 However, Ag-supported inorganic materials can overcome this disadvantage well. Up to now, zeolites, calcium phosphate, and carbon fiber have been developed as inorganic supports for antibacterial Ag-containing materials.30,31 Especially, Ag-supported silica materials, such as silica glass and silica thin films, are expected to be good candidates for antibacterial materials due to their fine chemical durability and high antibacterial activity.32-34 Core-shell or hybrid structures have been intensively studied very recently, in particular since such structures exhibit peculiar properties that make them attractive for applications in optical and biological sensors and in optoelectronics.35-37 Usually, identification of the different chemical states of elements can be easily carried out by X-ray photoelectron spectroscopy (XPS) because of shifting binding energy. Many groups have been investigated the chemical state of Ag with XPS, but they reported the position of binding energy or the ratio of Ag component in analytic systems.33,38,39 Specific O1s binding energies and chemical states of the Ag-SiO2 nanocomposite have not been published yet. Pawlak et al.40 reported that the nonsingular O1s peak that occurred in mixed perovskite crystals was due to polarization of the oxygen valence electron density. In this study, we report the chemical binding states of AgSiO2 nanocomposite and of prepared pure SiO2 nanoparticles. Our purpose is to report a detailed comparative XPS study of pure SiO2 and Ag-SiO2 nanocomposite and to see how the pure SiO2 nanoparticle differs from Ag-SiO2 nanocomposite. Also, we report that the antibacterial properties of Ag nanoparticles formed on the surface of SiO2 nanoparticles show very excellent

10.1021/jp068302w CCC: $37.00 2007 American Chemical Society Published on Web 02/09/2007

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Kim et al.

Figure 1. Tentative mechanism of Ag nanoparticles formed on the surface of SiO2 nanoparticle, with and without catalyst, and schematic diagram of chemical structure of Ag-SiO2 nanocomposite.

inhibitory effects on various microorganisms because of the ultrafine Ag nanoparticles homogeneously formed without aggregation on the surface of the SiO2 nanoparticle. Experimental Section Synthetic Method for Ag Formation on the Surface of SiO2 Nanoparticles. SiO2 nanoparticles were synthesized according to the well-known Stober method by hydrolysis and condensation of tetraethoxysilane (TEOS, Aldrich, 98%, 0.5 mol) in a mixture of ethanol (1000 mL) and water (1 mol), with ammonia solution (1 mol, assay from 28% to 30%, Junsei Co.) as catalyst to initiate the reaction. The size of SiO2 nanoparticles was controlled by the molar ratio of TEOS, water, and ammonia solution.41 Ultra-high-purity water (18 M, Millipore) was used throughout the whole experiment. The reaction started with mixing and stirring of the components, required for 6 h, and drying at a temperature below 100 C for 2 h. To form Ag nanoparticles on the surface of SiO2 nanoparticles, the specified amounts of silver nitrate (AgNO3, Aldrich, 97%) as given in Table 1 were added into SiO2 nanoparticle slurry, which was prepared by dissolving 50 mmol of SiO2 nanoparticles in water. We prepared Ag-SiO2-1, AgSiO2-2, Ag-SiO2-3, and Ag-SiO2-4 by adding 8.83 mmol of AgNO3 in the absence of catalyst, 2.65 mmol of AgNO3 in the
Figure 2. XP spectra of SiO2 and Ag-SiO2 nanocomposites: (a) Survey (1, Ag3d5/2; 2, Ag3d3/2; 3, Ag3p3/2; 4, Ag3p1/2; 5, O KL22L23; 6, O KL1L23; 7, Ag MV45V45). (b) O1s XP spectra of SiO2 and AgSiO2. The binding energy scale has been adjusted to C1s line at 285.1 eV. (c) Electron density of O in Si-O-Ag, Si-O-Si, and Si-O-H.

absence of catalyst, 8.83 mmol of AgNO3 in the presence of catalyst (105.28 mmol of ammonia solution), and 2.65 mmol of AgNO3 in the presence of catalyst (105.28 mmol of ammonia solution), respectively, into SiO2 nanoparticle slurry at room temperature for 6 h under vigorous stirring. The obtained products were filtered and purified by washing with ethanol and then dried at room temperature for 2 h. Characterization. The size and morphology of the products were studied by transmission electron microscopy (TEM; Hitachi H-7500). The elemental ratio of prepared nanocomposites was characterized by scanning electron microscopy-energydispersive X-ray spectrometry (SEM-EDX; Hitachi S-2400).

Antibacterial Ag-SiO2 Nanocomposite

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Figure 3. TEM images of (a) Ag-SiO2-1, (b) Ag-SiO2-2, (c) Ag-SiO2-3, and (d) Ag-SiO2-4 nanocomposites. All scale bars represent 97 nm.

TABLE 2: Core Level Binding Energies of Elementsa

binding energy, eV material Si2p O1s, Si-O-Ag O1s, Si-O-Si O1s, Si-O-H Ag3d5/2

SiO2 103.20 532.20 533.20

Ag-SiO2 103.22 530.20 532.27 533.26 368.43

Based on C1s at 285.1 eV.

Figure 4. Energy-dispersive X-ray spectra of Ag-SiO2 nanocomposites: (a) Ag-SiO2-1, (b) Ag-SiO2-2, (c) Ag-SiO2-3, and (d) AgSiO2-4.

Chemical analysis on the elements was recorded on an XPS (Multilab 2000). The samples were compressed into a pellet of 2 mm thickness and then mounted on a sample holder by utilizing double-sided adhesive tape for XPS analysis. The sample holder was then placed into a fast-entry air load-lock chamber without exposure to air and evacuated under vacuum (<10-6 Torr) overnight. Finally, the sample holder was transferred to the analysis chamber for XPS study. The base pressure inside the analysis chamber was usually maintained at better than 10-10 Torr. Binding energy was referenced to the C1s line at 285.1 eV from adventitious carbon.42 Curve deconvolution of the obtained XP spectra was performed with the XPS Peak Fitting Program (XPSPEAK41, Chemistry, CUHK).

Test of Antibacterial Properties. For antibacterial experimentation, Pseudomons aeruginosa (ATCC 17934, Gramnegative bacterium), Stphylococcus aureus (ATCC 25923, Gram-positive bacterium), Escherichia coli (ATCC 25922, Gram-negative bacterium), Enterobacter cloacae (ATCC 29249, Gram-negative bacterium), Candida albicans (ATTC 11282, yeast), Penicillium citrinum (ATCC 42504, fungus), and Aspergillus niger (ATCC 64958, fungus) were selected as indicators. All disks and materials were sterilized in an autoclave before experiments. The antibacterial activities of Ag-SiO2 nanocomposites were measured by two methods: paper disk diffusion assay and minimal inhibitory concentration (MIC).43-45 The disk diffusion assay was performed by placing a 8 mm disk saturated with 5000 g/mL Ag-SiO2-1, Ag-SiO2-2, AgSiO2-3, or Ag-SiO2-4 nanocomposite aqueous slurry onto an agar plate seeded with various microorganisms. After 24 h of incubation, the diameters of the inhibition zones were measured. MIC values were determined as the lowest concentration of AgSiO2-3 nanocomposite where the absence of growth was recorded. At the end of the incubation period, the plates were evaluated for the presence or absence of growth.

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TABLE 3: Ag, Si, and O Atomic Percentages of the Ag-SiO2 Nanocomposites
XPS analysis at. % material Ag-SiO2-1 Ag-SiO2-2 Ag-SiO2-3 Ag-SiO2-4 Ag 2.13 2.14 2.52 4.00 Si 26.25 24.51 26.25 23.88 O 71.23 73.35 71.23 72.12 Ag 2.00 2.20 2.70 4.31 at. % Si 37.40 36.89 38.83 32.95 O 60.60 60.91 58.47 62.74 Ag 9.65 10.55 12.55 19.41 EDX analysis wt % Si 46.98 46.10 47.07 38.66

Kim et al.

O 43.37 43.35 40.37 41.93

TABLE 4: Antibacterial Activities of Ag-SiO2 Nanocomposites against Various Bacteria, Fungi, and Yeasta
Ag-SiO2 (g/mL) microorganism Escherichia coli (N) Pseudomonas aeruginosa (N) Staphylococcus aureus (P) Enterobacter cloacae (N) Candida albicans (Y) Penicilium citrinum (F) Aspergillus niger (F)

0 + + + + + + +

100 + + + + + + +

200 + + + + + + +

300 + + + + +

500 + + + + +

1000 + + + -

2000 + + -

3000 -

5000 -

Key: +, antibacterial activity; -, antibacterial activity; P, Gram-positive bacterium; N, Gram-negative bacterium; F, fungus; and Y, yeast.

Results and Discussion Synthetic Method for Ag Formation on the Surface of SiO2 Nanoparticles. Alkaline condition produces strong nucleophiles that deprotonate hydroxyl ligands (-OH), and then these nucleophilic parts (-O-) react with electrophilic materials such as Ag, Cu, Au, etc. This mechanism is schematically illustrated in Figure 1. Ag-SiO2 nanocomposites with catalyst are synthesized by three steps. The first step is deprotonation of hydroxyl ligand in SiOH. Adding base catalyst into SiOH generates the SiO- group:

Si-O-H + B: f SiO- + BH
The second step is electrophilic attack. Electrophilic metal (Ag+) is easily bonded with the nucleophilic part (SiO-):

SiO- + Ag+ f SiO-Ag

The third step is growth of the Ag nanoparticles by attaching more Ag+ on the surface of the SiO2 nanoparticle. The Ag forming process we employed is considered to be sensitive to the configuration of terminal groups on the SiO2 surface, since such surface groups obviously provide the capability required for the reduction of Ag ions via reactions such as

Si-O-H + Ag+ f Si-O-Ag + H+

Terminal OH groups usually form on the oxide surface by dissociative adsorption of water molecules, depending on their coordination symmetry.46 Accordingly, nanocomposite may form by autoreduction of noble metal ions with oxide surfaces. The efficiency of the surface-mediated reduction process can be decreased with consumption of hydroxyl groups and generation of surface charging. A schematic diagram for a tentative mechanism of Ag deposition on the surface of SiO2 nanoparticles without catalyst is illustrated in Figure 1. The chemical states of elements in pure SiO2 nanoparticles and Ag-SiO2 nanocomposites were investigated by XPS. Figure 2 shows the representative survey of XP spectra of pure SiO2 and Ag formed on the surface of SiO2 nanoparticles (a) and the high-resolution XP spectra of O1s (b). The resulting Si2p spectrum shows a peak at binding energy 103.20 eV, in agreement with the accepted binding energy value for SiO2. The peaks at about 368.43 and 372.51 eV are attributed to Ag3d5/2

and Ag3d3/2, respectively. Table 2 summarizes the XPS binding energies of the elements in pure SiO2 and Ag-SiO2 nanocomposites. On the basis of the binding energies, it is clear that O1s binding energies of the Si-O-Si unit and Si-O-H unit in SiO2 nanoparticles in Figure 2b are observed at 532.20 and 533.20 eV, respectively. The O1s binding energy of the SiO-Ag unit in the Ag-SiO2 nanocomposite is observed at 530.20 eV. Pawlak et al.40 reported very useful information about interpretation of XPS data. In that report, the more ionic character the countercation has, the lower the binding energies of the framework elements are. In the case of the SiO2 nanoparticles, the valence electron of O will be more shifted toward the H in Si-O-H than toward Si in Si-O-Si. This phenomenon makes it more difficult to eject a core electron from O in Si-O-H than from O in Si-O-Si. Therefore, the binding energy of O1s in Si-O-H is observed at higher binding energy compared to that of O1s in Si-O-Si. In the case of Ag-SiO2 nanocomposite, the valence electron of O will be less shifted toward the Ag in Si-O-Ag than toward Si in Si-OSi. The electron density is greater near the O in Si-O-Ag than near the O in Si-O-Si, which makes it easier to eject a core electron from O in Si-O-Ag than from O in Si-O-Si. Therefore, the binding energy of O in Si-O-Ag is observed at lower binding energy compared to that of O in Si-O-Si. The influence of the amount of silver nitrate in the absence of catalyst is shown in Figure 3 a,b. To get the optimized ratio of Ag, the molar ratios of AgNO3 and catalyst were controlled. As the molar ratios of AgNO3 were increased, the amount of Ag nanoparticles formed on the surface of SiO2 was increased. Figure 3a,b shows TEM images of Ag nanoparticles with a diameter of less than 10 nm formed on the surface of SiO2 nanoparticles. In the case of Ag-SiO2-1 (Figure 3a), not many Ag nanoparticles are formed on the surface of the SiO2 nanoparticle, but in the case of Ag-SiO2-2 (Figure 3b), a few Ag nanoparticles are shown. In the presence of the catalyst, many Ag nanoparticles are formed on the surface of SiO2 nanoparticles, and the sizes of Ag nanoparticles in Ag-SiO2-3 (Figure 2c) and Ag-SiO2-4 (Figure 2d) are larger than those of Ag nanoparticles prepared without the catalyst (Ag-SiO2-1 and Ag-SiO2-2) despite the same reaction time. In particular, Ag nanoparticles of Ag-SiO2-3 are easily formed on the surface of SiO2 compared to those of Ag-SiO2-1 despite the same molar ratio of AgNO3, and the size of Ag nanoparticles of Ag-SiO2-3

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Figure 5. Photographs of antibacterial test results on (a) S. aureus, (b) P. aeruginosa, (c) C. albicans, (d) P. citrinum, and (e) A. niger incubated on plates. (f) Position 1 is Ag-SiO2-1, position 2 is AgSiO2-2, position 3 is Ag-SiO2-3, and position 4 is Ag-SiO2-4 nanocomposite dispersed in water.

Figure 6. Photographs of the antibacterial test results against (a-d) P. aeruginosa, E. coli, S. aureus, and E. cloacae and (e-g) C. albicans, P. citrinum, and A. niger. Amount of Ag-SiO2-3 nanocomposite used (micrograms per milliliter): (a) 200, (b) 300, (c) 500, (d) 3000, (e) 500, (f) 1000, and (g) 2000.

is larger than that of Ag-SiO2-1. The same trend is observed between Ag-SiO2-4 and Ag-SiO2-2. In the case of Ag- SiO23, homogeneous Ag nanoparticles are observed, but in the case of Ag-SiO2-4, Ag nanoparticles formed on the surface of SiO2 nanoparticles are aggregated and some Ag nanoparticles are independently formed. EDX analyses of Ag-SiO2 nanocomposites excited by an electron beam (20 keV) were performed. Peaks for the elements O, Si, and Ag are observed at 0.5249 (OkR1), 1.739 98 (SikR1,2), 1.835 94 (Sik1), 2.9843 (AgLR1), 2.9782 (AgLR2), 3.1509 (AgL1), and 3.3478 (AgL2), respectively. There are only Si, O, and Ag components in EDX spectra. From the EDX spectra (Figure 4 and Table 3), we can confirm that nanoparticles in TEM images are pure hybrid-type Ag-SiO2 nanocomposites. Table 3 shows that the atomicpercentage of Ag is increased from 2.00 to 4.31. Table 3 and Figure 3 show that the Ag nanoparticles are easily formed and well dispersed on the surface of SiO2 nanoparticles in the presence of a moderate amount of catalyst. The atomic percentages of Ag, Si, and O investigated with EDX and XPS show similar tendencies, as summarized in Table 3. Evaluation of Antibiotic Properties. It is suggested to be advantageous to enhance the antibacterial activity that strong adsorption ability causes both bacteria and part of the dispersed Ag nanoparticles to be adsorbed on the surface of SiO2 nanoparticle, where the bacteria have more opportunities to contact Ag nanoparticles. From this point of view, in order to avoid the aggregation of Ag nanoparticles, an optimum level of Ag nanoparticle loading is recommended for the synthesis of Ag formed on the surface of SiO2 nanoparticles for antibacterial activity. Antibacterial activities of Ag-SiO2 nanocomposites against microorganisms considered in the present study were qualitatively and quantitatively assessed by determining the presence of inhibition zones and MIC values,

respectively. Antibacterial effects in the form of inhibition zones, evaluated by the disk diffusion assay of the Ag-SiO2 nanocomposites, are shown in Figure 5. The clear zones of AgSiO2-3 against S. aureus (Gram-positive bacterium), P. aeruginosa (Gram-negative bacterium), C. albicans (yeast), P. citrinum (fungus), and A. niger (fungus) are determined as 0, 14, 11, 11.5, and 0 mm, respectively, but the symptoms of clear zones against S. aureus and A. niger are shown because the colors between microorganism and around disk are different.47 In the case of AgSiO2-1, Ag-SiO2-2, and Ag-SiO2-4, inhibition zones are clearly detected against P. aeruginosa but they are not detected against other microorganisms; however, in the case of AgSiO2-3, inhibition zones are clearly detected against P. aeruginosa, C. albicans, and P. citrinum. From these results and EDX and TEM images, the antibacterial properties are controlled by the molar ratio of Ag and dispersibility of Ag nanoparticles. As the molar ratio of Ag is increased, antibacterial properties are also increased except in the case of Ag-SiO2-4. In TEM images of Ag-SiO2-3 and Ag-SiO2-4, Ag-SiO2-3 showed better dispersibility of the Ag nanoparticles on the surface of the SiO2 nanoparticles, but Ag-SiO2-4 showed aggregation of Ag nanoparticles, despite the fact that the Ag atomic percentage of Ag-SiO2-4 was higher than that of AgSiO2-3. Aggregation of Ag nanoparticles causes deterioration of the antibacterial activity. It is obvious that the antibacterial activity will be improved greatly with increasing amount of Ag nanoparticles formed on the surface of SiO2 nanoparticles and the degree of dispersibility of Ag nanoparticles. Feng et al.48 reported a mechanistic study of the antibacterial effect of silver ions on E. coli and S. aureus. The first suggestion is the following; as a reaction against the denaturation effects of silver ions, DNA molecules become condensed and lose their replica-

3634 J. Phys. Chem. C, Vol. 111, No. 9, 2007 tion abilities. The second suggestion is that silver ions interact with thiol groups in proteins, which induces the inactivation of bacterial proteins. Besides the known antibacterial mechanism of Ag, this phenomenon may also be partially explained by the fact that Ag nanoparticles formed on the surface of SiO2 carry the opposite charge with Gram-negative bacteria, P. aeruginosa, thereby killing them more easily than Gram-positive bacteria due to the electrostatic attraction. The values of inhibition zones against fungi (P. citrinum and A. niger) and yeast (C. albicans) appear in the middle between the values of inhibition zones against Gram-positive (S. aureus) and Gram-negative (P. aeruginosa) bacteria. The growth inhibition effects for P. aeruginosa, S. aureus, E. coli, E. cloacae, C. albicans, P. citrinum, and A. niger were quantitatively determined by the MIC method for the AgSiO2-3 nanocomposite. Among the samples tested, high antibacterial activities against bacteria, fungi, and yeast even with low concentrations of Ag-SiO2-3 nanocomposite are shown in Figure 6 and Table 4. Especially, Ag-SiO2-3 nanocomposite exhibits high efficiency for the destruction of E. coli and P. aeruginosa, even with only 300 g/mL Ag-SiO2-3 nanocomposite (37.65 g/mL Ag nanoparticles). From EDX results, the exact concentration of Ag is calculated as 37.65 g/mL because 100 wt % Ag-SiO2 nanocomposite consists of 12.55 wt % Ag and 87.44 wt % SiO2. In the case of 2000 g/mL Ag-SiO2 nanocomposites (251 g/mL Ag), the antibacterial activities indicate good efficiency against all microorganisms used in this study because of the enhanced dispersibilty of Ag nanoparticles.49 From MIC results, we reconfirm that positively charged Ag nanoparticles are easily reacted with Gram-negative bacteria rather than Gram-positive bacteria, so that Gram-negative bacteria are more effectively killed than Gram-positive bacteria. Also, the degree of antibacterial activities of Ag-SiO2 nanocomposite against fungi and yeast appears in the middle range between Gram-positive and Gram-negative bacteria because of the above mechanism. Conclusion SiO2 formed with Ag nanoparticles was prepared at room temperature. This method will be well suited for preparing metal nanoparticles formed on the surface of SiO2 nanoparticles. As the ratio of AgNO3 was increased, the amount of Ag nanoparticles formed on the surface of SiO2 was increased. To easily form Ag nanoparticles on the surface of SiO2, use of a catalyst in the synthetic method was recommended because strong nucleophiles were produced by ammonia solution via deprotonation of hydroxyl ligands and then electrophilic material, like metal ions, reacted with nucleophilic sites. XPS measurement showed that O1s binding energies were affected by the atoms attached to O. The binding energy of O1s in Si-O-H was observed at higher values than that of O1s in Si-O-Si because of H atom decreasing the electron density of O (O-H), whereas the binding energy of O1s in Si-O-Ag was observed at lower binding energy than that of O1s in Si-O-Si because Ag atom increases the electron density of O (O-Ag). In the antibacterial test, the antibacterial activities of Ag-SiO2-3 were clearly detected against Gram-negative bacteria, Gram-positive bacteria, yeast, and fungi. The antibacterial activities of Ag-SiO2-3 nanocomposite were higher than those of Ag-SiO2-4 because Ag nanoparticles of Ag-SiO2-3 nanocomposite were homogeneously formed on the surface of SiO2 nanoparticle without aggregation of the Ag nanoparticles. Positively charged Ag nanoparticles killed Gram-negative bacteria more easily than Gram-positive bacteria.

Kim et al. Acknowledgment. Functional Chemicals Development Program and Thefaceshopkorea Co. Ltd. supported this work. We also appreciate financial support by the Brain Korea 21 project in 2006. References and Notes
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