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Article history: The modication of zeolite A (NaA) by impregnation with different concentrations of silver ions (Ag+) or silver
Received 26 July 2013 nanoparticles (AgNPs) for antibacterial activity was investigated. The Ag+NaA composites were prepared by ion
Received in revised form 16 May 2014 exchange against different concentrations of silver nitrate solution (25200 mg/L) while AgNPs were subsequently
Accepted 31 May 2014
prepared by reducing the impregnated Ag+ with sodium borohydride. The addition of Ag+ and AgNPs had no dis-
Available online 8 June 2014
cernible effect on the NaA structure. The AgNPs in the AgNPNaA composites exhibited a typical broad absorption
Keywords:
peak at 394 nm that was absent in the Ag+NaA composites. The Ag+NaA and AgNPNaA composites both
Silver ion showed a dose- and time-dependent antimicrobial activity against the Gram-positive Staphylococcus aureus and
Silver nanoparticle Gram-negative Escherichia coli bacteria, but were substantially more effective against E. coli than S. aureus. Moreover,
Zeolite A Ag+NaA composites had a substantially higher antibacterial efciency against E. coli than the AgNPNaA compos-
Antibacterial activity ites, whereas the highest concentration at 3 h, the AgNPNaA composites were weakly more effective than the Ag+
Nanocomposite NaA composites against S. aureus.
Impregnation 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.powtec.2014.05.049
0032-5910/ 2014 Elsevier B.V. All rights reserved.
D. Jiraroj et al. / Powder Technology 264 (2014) 418422 419
Fig. 1. X-ray diffractograms of pure zeolite A (NaA), Ag+NaA and AgNPNaA composites formed from different concentrations of AgNO3.
The antibacterial activity of the NaA and the respective Ag+NaA and
AgNPNaA composites was studied in terms of the reduction in the num-
ber of viable S. aureus (ATCC 6538) and E. coli (ATCC 25922) cells, as rep-
resentative Gram-positive and Gram-negative bacteria, respectively,
following exposure of a bacterial suspension (~1 107 colony-forming
units (CFU)/mL) to the compounds at 0.1 mg/mL for 1, 2 and 3 h at
37 C. Following exposure the number of viable bacteria was determined
by the total plate count method [19], using three replicate plates per cul-
ture dilution, and expressed relative to the number of viable bacteria
(CFU/mL) in the untreated control culture, which was set at 100% viable Fig. 2. DR-UV absorption spectra of pure zeolite A (NaA), Ag+NaA and AgNPNaA
(0% antibacterial activity). composites at the silver concentration of 200 mg/L.
420 D. Jiraroj et al. / Powder Technology 264 (2014) 418422
Fig. 3. Scanning electron micrographs (50,000) of (a) pure zeolite A (NaA), (b) Ag+NaA and (c) AgNPNaA composites.
of pure NaA [21,27,28] as illustrated in Fig. 1. Therefore, the incorpora- The morphology shown by scanning electron micrographs in Fig. 3,
tion of Ag+ or AgNP into the NaA at these ratios had no discernible sig- indicated that incorporation of Ag+ ions and AgNPs into NaA structure
nicant effect on the NaA structure. Generally, and in accordance with does not make any change in the size and shape of NaA, except for the
these results, the microporous NaA crystals are found in the [100] and increase of the surface roughness in the case of Ag+ ion, as seen in
[110] cubic formation [29]. Fig. 3(b). For microstructure analysis, the transmission electron micro-
Furthermore, the AgNPs in the AgNPNaA composites revealed the graphs in Fig. 4 showed the distribution of the Ag and AgNP in the struc-
typical broad absorption UV peak of spherical AgNPs at about 400 nm, ture of NaA as the dark contrast spots in the electron micrographs, as
due to their surface plasmon resonance [15,25,3033], AgNPNaA200, seen in Fig. 4(b) and (c) respectively, along with their selected area elec-
the representative maximum absorption peak was around 394 nm tron diffraction (SAED) patterns. From the transmission micrograph in
(Fig. 2). This suggests that the sizes of the AgNPs in the composites Fig. 4(b), the Ag+ ions were impregnated onto the surface of the NaA
were between 4 and 32 nm in diameter [15,24,26]. As expected, this especially at the brim of the zeolite A. This may induce an increase of
peak was not present in the Ag+NaA composites or the pure NaA the surface roughness for Ag+NaA samples, as seen in previous scan-
sample. ning electron micrograph (Fig. 3(b)). From SAED, we cannot see the
Previous work using hyaluronan to reduce the Ag+ ions to AgNPs re- change in the crystal structure of the NaA host due to the present of
vealed that increasing the hyaluronan to silver nitrate ratio, tempera- Ag+ and AgNP in NaA. Moreover, some Ag particles could precipitate
ture and pH value could all increase the rate of Ag+ reduction and the into the zeolite pores that can be noticed in Fig. 4(b) and (c). Some
obtained AgNP size, with a maximum absorption peak at around 400 AgNP in composites could be agglomerated. As a result, the Ag clusters
450 nm [34]. The estimated size of the AgNPs in the AgNPNaA compos- were formed and might provide the wider range of particle size distri-
ites in our case is around 410 nm which conrmed by transmission bution in the DR-UV spectrum of AgNPNaA composite.
electron micrographs. This is in agreement with a previous study that
reported AgNPs of 313 nm were deposited on montmorillonite clay 3.2. Antibacterial activity
[35]. The absorption peak of the AgNPNaA composites prepared from
the higher AgNO3 concentrations shifted to lower wavelengths (not The antibacterial activity of the different Ag+NaA and AgNPNaA
shown), which is due to the formation of smaller AgNPs [26,34,36]. composites, compared to NaA, was investigated against S. aureus and
Indeed, a broad absorbance band tailing at longer wavelengths is consis- E. coli as representative Gram-positive and Gram-negative bacteria, re-
tent with the increasing number of larger sized AgNPs [26]. In accor- spectively. The pure NaA sample had no signicant antibacterial activi-
dance, the DR-UV peak intensity of the AgNPNaA composites has ty, while the different Ag+NaA and AgNPNaA composites revealed a
the highest value for AgNPNaA200 followed by AgNPNaA100 N dose- and exposure time-dependent antibacterial activity against both
AgNPNaA50 N AgNPNaA25 (not shown). Thus, the peak intensity bacterial strains, but they were both signicantly more active against
of all Ag+NaA samples shows a very low value compare to those E. coli than S. aureus (Fig. 5).
AgNPNaA. This reects the balance between the net AgNP amount With respect to the apparent Ag+ or AgNP dose-dependence in the
(total area under the peak), particle size (wavelength) and size dis- respective NaA composites upon the antibacterial activity induced, a
tribution (tail). clear dose-dependent affect was seen for both silver types upon both
Fig. 4. Transmission electron micrographs of (a) pure zeolite A (NaA), (b) Ag+NaA and (c) AgNPNaA composites at the silver concentration of 200 mg/L, insert as SAED pattern.
D. Jiraroj et al. / Powder Technology 264 (2014) 418422 421
[6] M. Yu, M. Lin, C. Han, L. Zhu, C.J. Li, X. Yao, Ligand-promoted reaction on silver [22] S. Domnguez-Domnguez, A. Berenguer-Murcia, E. Moralln, A. Linares-Solano, D.
nanoparticles: phosphine-promoted, silver nanoparticle-catalyzed cyclization of Cazorla-Amors, Zeolite LTA/carbon membranes for air separation, Microporous
2-(1-hydroxy-3-aryprop-2-ynyl)phenols, Tetrahedron Lett. 51 (2010) 67226735. Mesoporous Mater. 115 (2008) 5160.
[7] L. Tang, C. Dong, J. Ren, Highly sensitive homogeneous immunoassay of cancer bio- [23] D.V. Quang, P.B. Sarawade, A. Hilonga, J.K. Kim, Y.H. Shim, G.N. Shao, H.T. Kim,
marker using silver nanoparticles enhanced uorescence correlation spectroscopy, Synthesis of silver nanoparticles within the pores of functionalized-free silica
Talanta 81 (2010) 15601567. beds: the effect of pore size and porous structure, Mater. Lett. 68 (2012) 350353.
[8] M. Larguinho, P.V. Baptista, Gold and silver nanoparticles for clinical diagnostics [24] A.R. Shahverdi, A. Fakhimi, H.R. Shahverdi, S. Minaian, Synthesis and effect of silver
from genomics to proteomics, J. Proteome 75 (2012) 28112823. nanoparticles on the antibacterial activity of different antibiotics against Staphylococcus
[9] Y. Lv, H. Liu, Z. Wang, S. Liu, L. Hao, Y. Sang, D. Liu, J. Wang, R.I. Boughton, Silver aureus and Escherichia coli, Nanomedicine: NBM 3 (2007) 168171.
nanoparticle-decorated porous ceramic composite for water treatment, J. Membr. [25] A. Chhatre, P. Solasa, S. Sakle, R. Thaokar, A. Mehra, Color and surface plasmon effects in
Sci. 331 (2009) 5056. nanoparticle systems: case of silver nanoparticles prepared by microemulsion route,
[10] P. Sanpui, A. Murugadoss, P.V.D. Prasad, S.S. Ghosh, A. Chattopadhyay, The antibac- Colloids Surf. A Physicochem. Eng. Asp. 404 (2012) 8392.
terial properties of a novel chitosanAg-nanoparticle composite, Int. J. Food [26] U.B. Jagtap, V.A. Bapat, Green synthesis of silver nanoparticles using Artocarpus
Microbiol. 124 (2008) 142146. heterophyllus Lam. seed extract and its antibacterial activity, Ind. Crop. Prod. 46
[11] L. Lv, Y. Luo, W.J. Ng, X.S. Zhao, Bactericidal activity of silver nanoparticles supported (2013) 132137.
on microporous titanosilicate ETS-10, Microporous Mesoporous Mater. 120 (2009) [27] S. Alfaro, C. Rodrguez, M.A. Valenzuela, P. Bosch, Aging time effect on the synthesis
304309. of small crystal LTA zeolites in the absent of organic template, Mater. Lett. 61 (2007)
[12] O. Akhavan, E. Ghaderi, Bactericidal effects of Ag nanoparticles immobilized on 46554658.
surface of SiO2 thin lm with high concentration, Curr. Appl. Phys. 9 (2009) [28] G.M.A. Khan, S.M.Y. Arafat, M.N. Reza, S.M.A. Razzaque, S. Alam, Linde Type-A zeolite
13811385. synthesis and effect of crystallization on its surface acidity, Indian J. Chem. Technol.
[13] X. Ren, X. Meng, D. Chen, F. Tang, J. Jiao, Using silver nanoparticle to enhance current 17 (2010) 303308.
response of biosensor, Biosens. Bioelectron. 21 (2005) 433437. [29] K. Cho, R. Ryoo, S. Asahina, C. Xiao, M. Klingstedt, A. Umemura, M.W. Anderson, O.
[14] O.D. Renedo, M.J.A. Martnez, A novel method for the anodic stripping voltammetry Terasaki, Mesopore generation by organosilane surfactant during LTA zeolite crys-
determination of Sb(III) using silver nanoparticle-modied screen-printed elec- tallization, investigated by high-resolution SEM and Monte Carlo simulation, Solid
trodes, Electrochem. Commun. 9 (2007) 820826. State Sci. 13 (2011) 750756.
[15] J.S. Kim, E. Kuk, K.N. Yu, J.H. Kim, S.J. Park, H.J. Lee, S.H. Kim, Y.K. Park, Y.H. Park, C.Y. [30] F. Mirzajani, A. Ghassempour, A. Aliahmadi, M.A. Esmaeili, Antibacterial effect of
Hwang, Y.K. Kim, Y.S. Lee, D.H. Jeong, M.H. Cho, Antimicrobial effects of silver nano- silver nanoparticles on Staphylococcus aureus, Res. Microbiol. 162 (2011) 542549.
particles, Nanomedicine: NBM 3 (2007) 95101. [31] M. Guzman, J. Dille, S. Godet, Synthesis and antibacterial activity of silver nanopar-
[16] G. Carja, Y. Kameshima, A. Nakajima, C. Dranca, K. Okada, Nanosized silver ticles against gram-positive and gram-negative bacteria, Nanomedicine: NBM 8
anionic clay matrix as nanostructured ensembles with antimicrobial activity, (2012) 3745.
Int. J. Antimicrob. Agents 34 (2009) 534539. [32] S. Kaviya, J. Santhanalakshmi, B. Viswanathan, J. Muthumary, K. Srinivasan, Biosyn-
[17] J.Y. Kim, K.J. Ihn, J.S. Na, Synthesis of silver nanoparticles within intercalated thesis of silver nanoparticles using citrus sinensis peel extract and its antibacterial
clay/polymer nanocomposite via in situ electron transfer reaction, J. Ind. Eng. activity, Spectrochim. Acta A Mol. Biomol. Spectrosc. 79 (2011) 594598.
Chem. 17 (2011) 248253. [33] M.K. Shukla, R.P. Singh, C.R.K. Reddy, B. Jha, Synthesis and characterization of agar-
[18] S.S. Mahapatra, N. Karak, Silver nanoparticle in hyperbranched polyamine: synthe- based silver nanoparticles and nanocomposite lm with antibacterial applications,
sis, characterization and antibacterial activity, synthesis and properties of crystalline Bioresour. Technol. 107 (2012) 295300.
silver nanoparticles supported in natural zeolite chabazite, Mater. Chem. Phys. 112 [34] N. Xia, Y. Cai, T. Jiang, J. Yao, Green synthesis of silver nanoparticles by chemical
(2008) 11141119. reduction with hyaluronan, Carbohydr. Polym. 86 (2011) 956961.
[19] N.S. Flores-Lpez, J. Castro-Rosas, R. Ramrez-Bon, A. Mendoza-Crdova, E. Larios- [35] P. Praus, M. Turicov, V. Machovi, S. tudentov, M., Synthesis of starch-stabilized
Rodrguez, M. Flores-Acosta, Synthesis and properties of crystalline silver nanopar- silver nanoparticles and their application as a surface plasmon resonance-based
ticles supported in natural zeolite chabazite, J. Mol. Struct. 1028 (2012) 110115. sensor of hydrogen peroxide, characterization of silver nanoparticles deposited on
[20] P. Payra, P.K. Dutta, in: S.M. Auerbach, K.A. Carrado, P.K. Dutta (Eds.), Handbook of montmorillonite, Appl. Clay Sci. 49 (2010) 341345.
Zeolite Science and Technology, Marcel Dekker Inc., New York, 2003, pp. 119. [36] P. Vasileva, B. Donkova, I. Karadjova, C. Dushkin, Synthesis of starch-stabilized
[21] H. Youssef, D. Ibrahim, S. Komarneni, Microwave-assisted versus conventional synthe- silver nanoparticles and their application as a surface plasmon resonance-
sis of zeolite A from metakaolinite, Microporous Mesoporous Mater. 115 (2008) based sensor of hydrogen peroxide, Colloids Surf. A Physicochem. Eng. Asp.
527534. 382 (2011) 202210.