Journal of Sol-Gel Science and Technology 32, 219222, 2004 c 2004 Kluwer Academic Publishers.

Manufactured in The United States.

Antimicrobial SolGel Coatings

B. MAHLTIG, D. FIEDLER AND H. BOTTCHER Gesellschaft zur F rderung von Medizin-, Bio- und Umwelttechnologien e.V., GMBU, o Postfach 520165, D-01317 Dresden, Germany, Tel.: +49-351-2695340; Fax: +49-351-2695341
dresden@gmbu.de

Abstract. The preparation and the releasing behavior of modied silica coatings, containing embedded biocides on textiles, were compared and assessed with regard to application parameters like antimicrobial efcacy, wash-out and long-term behavior. For this, silica layers with embedded silver, silver salts and biocidal quaternary ammonium salts (cetyltrimethylammoniumbromid and octenidine) were investigated. Both the growth of fungi and bacteria can be inhibited by coatings with embedded biocides. Especially by using octenidine, an excellent long-term inhibition of fungi growth can be reached. Keywords: silver, textile, silica, biocidal, leaching, controlled release 1. Introduction the silica to biocide ratio and by additives with pore or complex forming properties [7, 9]. Applications were tested for wood protection [7], for microbial protection of catheters [8] and for food preservation foils [9]. Now textiles are an actual target for antimicrobial equipments, e.g., for the protection against microbial contaminations of medical textiles, against biofouling of outdoor textiles or for diminishing perspiration odour in sportswear [10]. Recently, different special bres with incorpated silver (e.g. PadycareTM ) or organic biocides (e.g. AmicorTM ) were created but for many practical applications a simple antimicrobial postproduction coating of any common bre is desirable. Therefore, in this study the preparation and release behavior of silica coatings with embedded biocides on textiles were investigated. As biocides, embedded silver and biocidal quaternary ammonium salts (cetyltrimethylammoniumbromid CTAB and octenidine) were used. The results were compared and assessed with regard to parameters such as antimicrobial efcacy, wash-out and long-term behavior. 2. Experimental Section

Nowadays antimicrobial coatings are of practical interest to prevent biocontamination. Therefore, different solgel systems with antimicrobial properties have been developed in recent years: 1. Photoactive TiO2 coatings with permanent antimicrobial properties working only at UV exposure due to photomineralization processes at the surface [1]; 2. Polycationic coatings with permanent antimicrobial properties, e.g., resulting from hydrolysis products of long-chained tetraalkylammoniumsilanes [2]; 3. Temporary antimicrobial solgel coatings with embedded biocides and controlled release of biocides [3, 4]. A comparison of these systems reveals that controlled release systems offer the greatest chance for variation because inorganic biocides (e.g., Ag, Cu [5, 6] or boric acid [7]) as well as any organic biocides [8] can be embedded. Also combinations of different biocides can be co-immobilized in order to extend the antimicrobial efciency and to diminish the resistance risk. The releasing of biocides can be controlled by changing
To

whom all correspondence should be addressed.

The preparation of pure silica sol and the coating of textile fabrics (polyester/cotton) are described in the literature [11]. The biocidal additives (AgNO3

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Table 1. Overview on the prepared biocidal coatings and the % of leached biocide as function of leaching time in H2 Odest . Thermal Biocidal additive treatment of the Coating (10 wt-% in SiO2 ) coated fabrics ( C) A B C D E F AgNO3 AgNO3 AgNO3 Agcolloidal Octenidine CTAB 80 120 180 120 120 120 % of leached biocide after 1h 74 63 0.3 0 8 43 4 h 18 h 88 92 73 72 0.5 1.4 0.3 1.5 11 11 54

(99.5%), colloidal Ag 85131, CTAB (99.0%) from FLUKA, Octenidin from SYNTHON Wolfen) were dissolved or dispersed into the silica sols. The composition of the coatings, the thermal treatment in air and the degree of leaching with deionised H2 O at room temperature are listed in Table 1. The concentration of silver in the leaching solution was measured by ICP-OES spectroscopy (spectrometer Plasmaquant 110, Zeiss, Germany) and of the organic biocides by LC-MS (Agilent 1100). The optical properties of silver containing samples were investigated by UV/VIS spectroscopy in diffuse reection mode (array spectrometer MCS400, Zeiss, Jena). The fungicidal effect of textile samples was determined with Aspergillus niger spores inocculated onto potato-dextrose-agar-plates. After a contact time of 2 and 6 days the CFU (colony forming units) were counted. The bactericidal effect was evaluated with textile samples impregnated with standard nutrient I/ Merck containing E. coli bacteria. After impregnation, the samples were incubated in standard nutrient for 24 h at 30 C and placed on agar for 2 days. The number of CFU were determined by counting. The settlement of air-born germs was investigated on textile samples placed for 2 weeks under normal room climate. After incubation on agar plates for 2 days the germs were rinsed out with phosphate buffer (pH 7). The actual number of germs was determined microscopically by counting with a Neubauer counting chamber. The rate of inhibition IR = 100 (100cS /cR ) was calculated with cR and cS as the number of CFU of sample and reference, respectively.

Figure 1. UV/vis-spectra of the silver containing coatings A to D on CO/PES textiles, measurement in diffuse reection mode.

3.

Results and Discussion

The releasing behavior of silica coatings on CO/PES textiles with embedded silver and silver salts are

compared with organic biocidal ammonium compounds in Table 1 and correlated with their antimicrobial properties. The coatings A to C result from the embedding of AgNO3 and different thermal posttreatment. In the case of A and B, more than 60% of the biocide is released in the rst hour of washing, while with C even after 18 h only 1.4% is released. The coating C is thermally treated at 180 C and by a thermal reduction of AgNO3 with residual ethanol which is present in the gel, the formation of colloidal silver can be expected [12]. This expectation is supported by the UV/VIS-spectra of the coatings, which show a clear minimum in reection around = 420 nm due to the plasmon resonance of colloidal silver [12] (Fig. 1). Moreover, the silver formation was observed by XRD investigations [13]. In case of thermal treatment at 80 C or 120 C the minimum in reection is less signicant, so a smaller amount of AgNO3 should be converted to silver. The most AgNO3 is still present in the coating and could be released easily due to the good solubility of AgNO3 in water. Another indication of the reaction with ethanol is that no coloration is observed for the analogous sols containing AgNO3 , if the ethanol is substituted by water before coating on glass. Coating D prepared with colloidal silver shows the same releasing behavior as coating C. The organic biocide CTAB exhibits a release of more than 40% in the rst hour of leaching, due to the good solubility of CTAB in water but the release is considerablely slowed down due to diffusion controlled processes from sub-surface regions [14]. In contrast, octenidine exhibits good solubility in ethanol but less in water. Therefore, only 8% of this biocide is released after 18 h of washing.

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Figure 2. Inhibition of fungi (Aspergillus niger). Figure 3. Inhibition of bacteria (E. coli).

Because of the high fungicidal effect of quarternary ammonium salts, the coatings E and F show a high inhibition rate of more than 90% against Aspergillus niger (Fig. 2). Due to the low degree of leaching of octenidine, the fungicidal effect of coating E is stable even after 18 h of leaching. In case of coating F containing the very soluble biocide CTAB, the inhibition rate decreased signicantly as a function of leaching time. Silver compounds are known to have a lesser fungicidal effect, so for the coatings A to C only inhibition rates in the range of 65 to 80% were observed (Fig. 2). The inhibition rates are nearly constant with the duration of leaching. Even after 18 h of leaching, enough silver should be present in the coating to inhibit fungal growth. The bacterial growth of E. coli can only be prevented signicantly by the coatings A, B and E, but with release of the biocides during leaching the inhibition rates are drastically decreased (Fig. 3). The coatings A and B contain a high amount of soluble silver compounds with strong bactericidal effect. By leaching, these silver compounds are removed from the textile and the bactericidal effect is decreased. Even the coating E with a smaller release of the biocide octenidine shows a signicant decrease of inhibition rate. The antimicrobial effect against unspecic air germs is an important parameter with regard to common uses of textiles. The settlement of air born germs is signicantly decreased by coatings A, B, C, E and F (Fig. 4). Even after 18 h of leaching, coatings E and F (containing organic biocides) retain sufcient biocide to exhibit inhibition rates of more than 90%. In spite of the

Figure 4. Inhibition of air born germs.

signicant release of CTAB from coating F, the remaining CTAB on the textile is able to prevent the settlement of germs. The coatings A to C exhibit high inhibition rates against air born germs, although coating A lose its efcacy after long-term leaching due to the high degree of leaching of silver from this coating. In contrast to this, the biocidal effect of coating D is small and could be explained by the small release of biocidal silver from this coating. For practical applications, a high biocidal effect and also a long-term stability of the coatings against leaching is required. A high efcacy and long-term stability is given for coatings with embedded octenidine.

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A lesser efcacy, but good long-term stability is observed for coating C containing silver resulting from embedded AgNO3 and a subsequent thermal treatment at 180 C. Both coatings could offer a perspective for practical application of antimicrobial solgel coatings on textiles. Due to these results, it is not surprising that the commonly-encountered embedding of silver and biocidal ammonium compounds within silica yields antimicrobial coatings with high biocidal efcacy and long-time stability [15]. 4. Conclusions

tions, we are very much indebted to Dr. Rapp and Mr. Burkhardt (Beiersdorf, Hamburg). References
1. T. Watanabe et al., Photocatalytic Purication and Treatment of Water and Air, edited by D. Ollis and H. El-Akabi (Elsevier, New York, 1993), p. 747. 2. A.J. Isquith, E.A. Abbott, and P.A. Walters, Appl. Microbiol. 24, 859 (1972). 3. H. B ttcher, K.-H. Kallies, and C. Roth, German Patent o DE4329279 (1993). 4. H. B ttcher, J. Prakt. Chem. 334, 14 (1992). o 5. C.C. Trapalis, M. Kokkoris, and G. Kordas, J. Sol-Gel Sci. Techn. 26, 1213 (2003). 6. M. Kawashita, S. Tsuneyama, F. Miyaji, T. Kokubo, H. Kozuka, and K. Yamamoto, Biomaterials 21, 393 (2000). 7. H. B ttcher, C. Jagota, J. Trepte, K.-H. Kallies, and H. Haufe, o Journal of Controlled Release 60, 57 (1999). 8. H. B ttcher, Mat.-Wiss. Werkstofftechn. 32, 759 (2001). o 9. H. B ttcher, K.-H. Kallies, and H. Haufe, J. Sol-Gel Sci. Techn. o 8, 651 (1997). 10. H. Mucha, D. H fer, S. Afalg, and M. Swerev, Melliand Texo tilberichte 82, 238 (2002). 11. B. Mahltig and H. B ttcher, J. Sol-Gel Sci. Techn. 27, 43 (2003). o 12. W. Li, S. Seal, E. Megan, J. Ramsdell, K. Scammon, L. Lelong, L. Lachal, and K.A. Richardson, J. Appl. Phys. 93, 9553 (2003). 13. D. Meyer, A. Levin, and B. Mahltig, to be published. 14. H. B ttcher, P. Slowik, and W. S , J. Sol-Gel Sci. Techn. 13, o u 277 (1998). 15. H. B ttcher, S. Sawusch, and K.-H. Kallies, German Patent DE o 199 35 230 (1999).

The biocidal effect of solgel coatings with embedded biocides on textiles was presented and compared to their release behavior. An inhibition of fungi and bacteria was observed for all coatings with embedded silver, silver salts and quarternary ammonium salts. Due to their high biocidal effect and long-term stability, for practical applications coatings with the biocide octenidine or silver resulting from embedded AgNO3 and thermal treatment of 180 C should be favoured. Acknowledgments We are grateful to the Bundesministerium f r Arbeit u und Wirtschaft (ANNA-project, Reg.-No. 59/03) for nancial support. For supporting LC-MS investiga-