Kayano Sunada

Studies on photokilling of bacteria on TiO2 thin film

In order to elucidate the mechanism for photokilling of Escherichia coli (E. coli) cells on titanium dioxide (TiO2) thin film, the survival of intact cells and the spheroplasts was investigated as a function of photo-illumination time. The photokilling reaction for intact cells was observed to involve two steps, an initial lower rate photokilling step followed by a higher rate one. In contrast, the reaction for spheroplasts, which do not have cell wall, exhibited only a single step kinetics with a higher rate, suggesting that the cell wall of E. coli cell acts as a barrier to the photokilling process. Changes in concentration of the cell wall components during illumination further showed that the outer membrane serves as a barrier, while the peptidoglycan layer does not have a barrier function. Moreover, atomic force microscopy measurements of cells on illuminated TiO2 film showed that the outer membrane decomposed first, and with further illumination, the cells completely decomposed. These results suggest that the photokilling reaction is initiated by a partial decomposition of the outer membrane, followed by disordering of the cytoplasmic membrane, resulting in cell death.

Photocatalytic bactericidal effect of TiO2 thin films: dynamic view of the active oxygen species responsible for the effect

The role of active oxygen species in the photocatalytic bactericidal effect was investigated using a thin transparent titanium dioxide (TiO2) film. The viable number of Escherichia coli (E. coli) significantly decreased on the illuminated TiO2 film, and the bactericidal effect was observed even when E. coli was separated from the TiO2 surface with a 50 μm porous membrane. Mannitol, a hydroxyl radical scavenger, inhibited the effect only in the absence of the membrane. In contrast, catalase inhibited the effect in all cases. On the basis of these results, the long-range bactericidal effect of hydrogen peroxide was proposed, together with a cooperative effect due to other oxygen species.

Hybrid Cu(x)O/TiO₂ nanocomposites as risk-reduction materials in indoor environments.

Photocatalytic TiO(2) powders impart ultraviolet light-induced self-cleaning and antibacterial functions when coated on outdoor building materials. For indoor applications, however, TiO(2) must be modified for visible-light and dark sensitivity. Here we report that the grafting of nanometer-sized Cu(x)O clusters onto TiO(2) generates an excellent risk-reduction material in indoor environments. X-ray absorption near-edge structure using synchrotron radiation and high-resolution transmission electron microscopic analyses revealed that Cu(x)O clusters were composed of Cu(I) and Cu(II) valence states. The Cu(II) species in the Cu(x)O clusters endow TiO(2) with efficient visible-light photooxidation of volatile organic compounds, whereas the Cu(I) species impart antimicrobial properties under dark conditions. By controlling the balance between Cu(I) and Cu(II) in Cu(x)O, efficient decomposition and antipathogenic activity were achieved in the hybrid Cu(x)O/TiO(2) nanocomposites.

Visible-Light-Sensitive Photocatalysts: Nanocluster-Grafted Titanium Dioxide for Indoor Environmental Remediation

Photocatalytic degradation of organic compounds requires photoexcited holes with strong oxidative power in the valence band (VB) of semiconductors. Although numerous types of doped semiconductors, such as nitrogen-doped TiO2, have been studied as visible-light-sensitive photocatalysts, the quantum yields of these materials were very low because of the limited oxidation power of holes in the nitrogen level above the VB. Recently, we developed visible-light-sensitive Cu(II) and Fe(III) nanocluster-grafted TiO2 using a facile impregnation method and demonstrated that visible-light absorption occurs at the interface between the nanoclusters and TiO2, as electrons in the VB of TiO2 are excited to the nanoclusters under visible-light irradiation. In addition, photogenerated holes in the VB of TiO2 efficiently oxidize organic contaminants, and the excited electrons that accumulate in nanoclusters facilitate the multielectron reduction of oxygen. Notably, Cu(II) and Fe(III) nanocluster-grafted TiO2 photocatalyst has the highest quantum yield among reported photocatalysts and has antiviral, self-cleaning, and air purification properties under illumination by indoor light fixtures equipped with white fluorescent bulbs or white light-emitting diodes.

Photocatalytic activity of Cu2+/TiO2-coated cordierite foam inactivates bacteriophages and Legionella pneumophila

Abstract We investigated the antiviral activity of TiO2-coated cordierite foam used in air cleaners, as well as the evaluation methodology. Furthermore, we developed Cu2+/TiO2-coated cordierite foam and investigated the reduction in viral infection ratio. The method for evaluation of antibacterial activity of TiO2-coated cordierite foam could also be applied to evaluation of antiviral activity. We showed that Cu2+/TiO2-coated cordierite foam reduced the viral infection ratio to a greater extent than TiO2-coated cordierite foam. Our findings suggest that the infection risk by polluted air could be decreased using Cu2+/TiO2-coated cordierite foam in air cleaners.

Highly efficient antiviral and antibacterial activities of solid-state cuprous compounds.

We found that several solid-state cuprous compounds, including cuprous oxide (Cu(2)O), sulfide (Cu(2)S), iodide (CuI), and chloride (CuCl), have highly efficient antiviral activities, whereas those of solid-state silver and cupric compounds are markedly lower. On a Cu(2)O-loaded glass substrate, for example, the infectious activity of bacteriophages was reduced by 5-orders of magnitude within 30 min and by 3-orders of magnitude within 1h for bacteria. In contrast, the infectious activities of both phages and bacteria were not markedly reduced on CuO-loaded substrates within a similar time frame. To determine the origin of this inhibitory activity, we investigated the effects of reactive oxygen species (ROS), leached copper ions, and the solid-state compound itself against bacteriophages, and concluded that infectious activity is lost following direct contact with the solid-state surface of cuprous compounds, but not ROS or copper ions. Furthermore, we found that Cu(2)O adsorbed and denatured more proteins than CuO, which suggests the difference of the inhibitory activity between Cu(2)O and CuO.

Detoxification of phytotoxic compounds by TiO2 photocatalysis in a recycling hydroponic cultivation system of asparagus.

TiO 2 photocatalytic decomposition and detoxification of phytotoxic compounds released by the roots of asparagus ( Asparagus officinalis L.) were investigated from the viewpoint of conservation-oriented cultivation. The phytotoxically active fraction was extracted either from dried asparagus roots or from the recycled nutrient solution of an asparagus hydroponic cultivation system. We found that the phytotoxic activity gradually decreased in the fraction with TiO 2 powder under irradiation with ultraviolet (UV) light at an intensity of 1.0 mW/cm (2). The growth of asparagus plants under actual cultivation conditions was also investigated by comparing asparagus grown in a hydroponic system where recycled waste nutrient solution was photocatalytically treated with solar light and a system with untreated recycled waste nutrient solution. The results showed, as measured by growth indices such as stem length and stem thickness, that asparagus growth in the photocatalytically treated system was superior to the untreated one. Furthermore, the yield of asparagus spears was 1.6-fold greater in the photocatalytically treated system, demonstrating the detoxification effect on the phytotoxic compounds and also the killing effect on pathogenic microorganisms.

Visible-light sensitive Cu(II)–TiO2 with sustained anti-viral activity for efficient indoor environmental remediation

Visible-light sensitive photocatalysts are desirable for indoor environmental remediation applications. Photocatalysts used for indoor environmental applications must have efficient visible-light activity and sustainable function under dark conditions, as indoor light instruments are typically switched off during the night. Herein, we report the synthesis and optimization of a highly visible-light sensitive Cu(II)–TiO2 nanocomposite with sustained anti-viral activity under dark conditions. The synthesized Cu(II)–TiO2 exhibited superior volatile organic compound decomposition and anti-viral activity under visible-light irradiation. Its quantum efficiency for the decomposition of gaseous 2-propanol reached 68.7%. In addition, Cu(II)–TiO2 completely inactivated the bacteriophage within 30 min of visible-light irradiation. Notably, the Cu(II)–TiO2 photocatalyst also exhibited sustained anti-viral activity under dark conditions after visible-light irradiation treatment. Taken together, these findings indicate that the prepared Cu(II)–TiO2 is potentially an effective risk-reduction material for indoor applications.

Comparison of the antiviral effect of solid-state copper and silver compounds.

Abstract Antiviral activities of insoluble solid-state and soluble ionic copper and silver compounds were evaluated against influenza A virus (A/PR8/H1N1) possessing a viral envelope and bacteriophage Qβ lacking an envelope. The viral solutions were exposed on glass samples uniformly loaded with copper and silver compounds. Exposure to solid-state cuprous oxide (Cu2O) efficiently inactivated both influenza A virus and bacteriophage Qβ, whereas solid-state cupric oxide (CuO) and silver sulfide (Ag2S) showed little antiviral activity. Copper ions from copper chloride (CuCl2) had little effect on the activity of bacteriophage Qβ in spite of the fact that copper ions strongly inactivate influenza A in previous studies. Silver ions from silver nitrate (AgNO3) and silver(I) oxide (Ag2O) in solution showed strong inactivation of influenza A and weak inactivation of bacteriophage Qβ. We also investigated the influence of the compounds on the function of two influenza viral proteins, hemagglutinin and neuraminidase. Silver ions from AgNO3 and Ag2O remarkably decreased enzymatic activity of neuraminidase through the breakage of disulfide (SS) bonds, corresponding to the selective inactivation of influenza A virus. By contrast, exposure to Cu2O markedly reduced the activity of hemagglutinin rather than neuraminidase. These findings suggest that solid-state Cu2O disrupts host cell recognition by denaturing protein structures on viral surfaces, leading to the inactivation of viruses regardless of the presence of a viral envelope.