Biocide mechanism of highly efficient and stable antimicrobial surfaces based on zinc oxide-reduced graphene oxide photocatalytic coatings.

Highly efficient photoactive antimicrobial coatings were obtained using zinc oxide-reduced graphene oxide nanocomposites (ZnO-rGO). Their remarkable antibacterial activity and high stability demonstrated their potential use for photoactive biocide surfaces. The ZnO-rGO nanocomposites were prepared by the sol-gel technique to create photocatalytic surfaces by spin-coating. The coatings were deeply characterised and several tests were performed to assess the antibacterial mechanisms. rGO was homogeneously distributed as thin sheets decorated with ZnO nanoparticles. The surface roughness and the hydrophobicity increased with the incorporation of graphene. The ZnO-rGO coatings exhibited high activity against the Gram-positive bacterium Staphylococcus aureus. The 1 wt% rGO coated surfaces showed the highest antibacterial effect in only a few minutes of illumination with up to 5-log reduction in colony forming units, which remained essentially free of bacterial colonization and biofilm formation. We demonstrated that these coatings impaired the bacterial cells due to cell membrane damage and intracellular oxidative stress produced by the photogenerated reactive-oxygen species (ROS). The enhancement of the ZnO photocatalytic performance upon rGO incorporation is due to the increased detected generation of hydroxyl radicals, attributed to the reduction of electron-hole pair recombination. This intimate contact between both components also conveyed stability against zinc leaching and improved the coating adhesion.

Antimicrobial surfaces with self-cleaning properties functionalized by photocatalytic ZnO electrosprayed coatings.

Photoactive coatings of sol-gel ZnO suspensions were electrosprayed on glass substrates to produce self-cleaning antimicrobial functionalized surfaces. ZnO-functionalized materials exhibited a uniform external surface consisting of a pattern of microspheres with diameters in the 100-300 nm range. Electrospray allowed surface densities up to 0.30 mg cm-2 that displayed considerable hydrophilicity. Water contact angle decreased with UV irradiation to values below 10°. Two different UV doses were tested by adjusting the irradiation time to simulate Summer-Spring and Winter-Fall conditions. The functionalized coatings showed excellent photocatalytic properties towards the photodegradation of Methylene blue. The electrosprayed surfaces also displayed antibacterial activity against Staphylococcus aureus, with >99.5% reduction in the number of culturable cells. The biocidal activity is attributed to the photogenerated reactive oxygen species on the surface of ZnO coatings and the bioavailable zinc ions produced from ZnO dissolution. The photoactive coatings kept surfaces free from bacterial colonization and biofilm formation.

Antimicrobial and antibiofilm efficacy of self-cleaning surfaces functionalized by TiO2 photocatalytic nanoparticles against Staphylococcus aureus and Pseudomonas putida.

A photocatalytic sol of TiO2 nanoparticles has been used for creating self-cleaning antimicrobial flat and porous glass surfaces. The substrates were irradiated to study their photocatalytic properties and behavior in the presence of biofilm-forming bacteria. Smooth glass surfaces and glass microfiber filters were covered with 1.98×10-3±1.5×10-4gcm-2 and 8.55×10-3±3.0×10-4gcm-2 densities, respectively. Self-cleaning properties were analyzed using the methylene blue 365nm UV-A photodegradation test. TiO2-coated filters achieved rapid and complete photodegradation of methylene blue because of the better TiO2 dispersion with respect to the glass slides. The effect of functionalized surfaces on the growth and viability of bacteria was studied using the strains Staphylococcus aureus and Pseudomonas putida. After irradiation (2h, 11.2Wm-2, 290-400nm), the initially hydrophobic surface turned hydrophilic. The antibacterial effect led to extensive membrane damage and significant production of intracellular reactive oxygen species in all TiO2-loaded irradiated specimens. The reduction of cell viability was over 99.9% (>3-log) for TiO2 on glass surfaces. However, the polymeric extracellular matrix formed before the irradiation treatment was not removed. This study highlights the importance of bacterial colonization during dark periods and the difficulty of removing the structure of biofilms.

Effect of water composition on the photocatalytic removal of pesticides with different TiO2 catalysts.

The objective of this work is double-firstly to explore the photocatalytic efficiency of five different commercial TiO2 catalysts in the photodegradation of a mixture of pesticides classified by the EU as priority pollutants and secondly to analyze the correlation between their physicochemical properties and the inhibition of the studied photocatalytic process when natural water was employed. Photocatalytic efficiencies when ultrapure water was used seem to point out that surface area was not a prerequisite for the photodegradation of the selected mixture of pesticides. On the other hand, significant differences in total organic carbon (TOC) conversions were obtained with the two studied water compositions. On one side, Evonik materials appear to be mostly inhibited when natural water was employed, whereas on the other, it should be remarked that anatase Sigma-Aldrich (SA) and, particularly, Hombikat UV100 (HBK) materials presented a very limited photo-efficiency inhibition or even a higher initial rate of TOC removal when a natural water matrix was used, probably due to their specific surface properties (PZC, S BET). Therefore, heterogeneous photocatalysis has proved to be a promising technology for the degradation of the selected mixture of pesticides where the final photo-efficiency of the five commercial titania catalysts studied here responds to a complex balance between its surface and structural properties.