Development of a novel conservation treatment of stone monuments with bioactive nanocomposites

In this study a conservation treatment of stone monuments meant for consolidation, protection, and inhibition of biofilm formation is proposed. The method is developed as a part of a systematic investigation aimed at producing nanocomposite coatings able to exert a marked biological activity over a long period of time thanks to their peculiar structure. Zinc oxide nanoparticles, synthesised by means of simple and reproducible electrochemical procedures, are embedded in commercially available and commonly used consolidant/water repellent matrices to obtain nanostructured materials. Products based on tetraethoxysilane and/or polysiloxanes were tested. In a first step the nanomaterials were applied on stone samples and studied with scanning electron microscopy and spectrophotocolorimetry. Then, in situ experimentation was undertaken by applying nanocomposite coatings on the exterior of a 12th-century church in the south of Italy. The performances of the ZnO-nanoparticles based composite coating were compared with a previously investigated copper nanoparticles based material, successfully tested and monitored in situ for more than two years. Finally, preliminary tests on the inhibitory effect on the growth of the fungus Aspergillus niger were also carried out. The results showed that in case of zinc oxide a tenfold higher concentration of nanoparticles as compared with Cu-NPs can be utilized in the matrices without affecting the colour of the stone substrate, which means that the new material should be able to exert a long-lasting biocide activity. Laboratory and in situ tests of the developed innovative nanomaterials yielded very promising, though preliminary, results in terms of chromatic changes, morphological characteristics and bioactivity. Constant monitoring of the coatings will be continued in order to obtain all necessary information on their long term behaviour and inhibition of biological colonisation.

[1]  T. V. Venkatesha,et al.  A hybrid electrochemical–thermal method for the preparation of large ZnO nanoparticles , 2010 .

[2]  D. J. Krause,et al.  The antimicrobial action of zinc ion/antioxidant combinations , 1992, Journal of clinical pharmacy and therapeutics.

[3]  Rajagopalan Vijayaraghavan,et al.  Enhanced bioactivity of ZnO nanoparticles—an antimicrobial study , 2008, Science and technology of advanced materials.

[4]  Ehud Banin,et al.  Synthesis and characterization of zinc/iron oxide composite nanoparticles and their antibacterial properties , 2011 .

[5]  Min Wei,et al.  Controllable preparation of Nano-MgO and investigation of its bactericidal properties. , 2005, Journal of inorganic biochemistry.

[6]  T. Mccarthy,et al.  Effects of copper and zinc ions on the germicidal properties of two popular pharmaceutical antiseptic agents cetylpyridinium chloride and povidone-iodine. , 1998, The Analyst.

[7]  Nele De Belie,et al.  Evaluation of strategies to prevent algal fouling on white architectural and cellular concrete , 2009 .

[8]  L. Sabbatini,et al.  Characterization and behaviour of ZnO-based nanocomposites designed for the control of biodeterioration of patrimonial stoneworks , 2015 .

[9]  T. Trindade,et al.  Antibacterial paper based on composite coatings of nanofibrillated cellulose and ZnO , 2013 .

[10]  P. Zambonin,et al.  Synthesis, analytical characterization and bioactivity of Ag and Cu nanoparticles embedded in poly-vinyl-methyl-ketone films , 2005, Analytical and bioanalytical chemistry.

[11]  N. Cioffi,et al.  Synthesis and analytical characterisation of copper-based nanocoatings for bioactive stone artworks treatment , 2011, Analytical and bioanalytical chemistry.

[12]  F. Marciano,et al.  Antibacterial activity of DLC films containing TiO2 nanoparticles. , 2009, Journal of colloid and interface science.

[13]  G. Oskam,et al.  Antifungal coatings based on Ca(OH)2 mixed with ZnO/TiO2 nanomaterials for protection of limestone monuments. , 2013, ACS applied materials & interfaces.

[14]  Mccarthy Tj,et al.  Effects of copper and zinc ions on the germicidal properties of two popular pharmaceutical antiseptic agents cetylpyridinium chloride and povidone-iodine , 1998 .

[15]  Claire Moreau,et al.  Water-repellent and biocide treatments: Assessment of the potential combinations , 2008 .

[16]  P. Maravelaki-Kalaitzaki,et al.  TiO2–SiO2–PDMS nano-composite hydrophobic coating with self-cleaning properties for marble protection , 2013 .

[17]  Shaimaa M. Fadel,et al.  Use of ZnO nanoparticles for protecting oil paintings on paper support against dirt, fungal attack, and UV aging , 2014 .

[18]  Filomena De Leo,et al.  Evaluation of the efficiency of water-repellent and biocide compounds against microbial colonization of mortars☆ , 2007 .

[19]  N. Cioffi,et al.  Electrosynthesized Polystyrene Sulphonate-Capped Zinc Oxide Nanoparticles as Electrode Modifiers for Sensing Devices , 2014 .

[20]  C. Karunakaran,et al.  Antibacterial and photocatalytic activities of sonochemically prepared ZnO and Ag–ZnO , 2010 .

[21]  S. Yun,et al.  Antibacterial activity of ZnO nanoparticles prepared via non-hydrolytic solution route , 2010, Applied Microbiology and Biotechnology.

[22]  A. Manna,et al.  Antibacterial activity of ZnO nanoparticle suspensions on a broad spectrum of microorganisms. , 2008, FEMS microbiology letters.

[23]  A. Gedanken,et al.  Antifungal activity of ZnO nanoparticles—the role of ROS mediated cell injury , 2011, Nanotechnology.

[24]  Lina Ghibelli,et al.  Copper Nanoparticle/Polymer Composites with Antifungal and Bacteriostatic Properties , 2005 .

[25]  M. Sundrarajan,et al.  Functionalization of cotton fabric with PVP/ZnO nanoparticles for improved reactive dyeability and antibacterial activity , 2012 .

[26]  Barbara Salvadori,et al.  Monitoring the performance of innovative and traditional biocides mixed with consolidants and water-repellents for the prevention of biological growth on stone. , 2012, The Science of the total environment.

[27]  A. B. Blazquez,et al.  Evaluation of the effect of some biocides against organisms isolated from historic monuments , 2000 .

[28]  K. Leeming,et al.  The use of immobilised biocides for process water decontamination , 2002 .

[29]  Yulong Ding,et al.  Mechanistic investigation into antibacterial behaviour of suspensions of ZnO nanoparticles against E. coli , 2010 .

[30]  F. Ahmad,et al.  Evaluation of the toxicity of ZnO nanoparticles to Chlorella vulgaris by use of the chiral perturbation approach , 2014, Analytical and Bioanalytical Chemistry.

[31]  P. Zambonin,et al.  Antifungal activity of polymer-based copper nanocomposite coatings , 2004 .