Ultraviolet irradiation of titanium dioxide in aqueous dispersion generates singlet oxygen
Open accessAbstract
We previously reported that irradiation of titanium dioxide (TiO2) in ethanol generates both singlet oxygen (1O2) and superoxide anion (O2*-) as measured by EPR spectroscopy. The present study describes the production of reactive oxygen species upon irradiation of TiO2 in aqueous suspension as determined by EPR spectroscopy using 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TMP) and 5,5-dimethyl-pyrroline-N-oxide (DMPO). Photoproduction of 1O2 by suspended TiO2, detected as 2,2,6,6-tetramethyl-4-piperidone-N-oxyl (4-oxo-TEMPO), was measured in water and deuterium oxide (D2O) in the presence or absence of sodium azide (NaN3) and under air or argon atmospheres. Production of a DMPO-OH adduct was examined in 4-oxo-TMP containing medium in the presence or absence of dimethyl sulfoxide (DMSO). The signal for the DMPO spin adduct of superoxide anion was not observed in aqueous conditions. Kinetic analysis revealed that 1O2 was produced at the surface of irradiated TiO2 in aqueous suspension as was observed in ethanol. Kinetic analysis revealed that the formation of DMPO-OH adduct reflects oxidation of DMPO by 1O2 rather than the trapping of the hydroxyl radical produced by the reaction of photo-exited TiO2 and water. The production of large amounts of 1O2 by TiO2 in aqueous suspension as compared to those in ethanol and possible formation of hydroxyl radical in aqueous suspension but not in alcohol, suggest that irradiation of TiO2 in aqueous environments is biologically more important than that in non-aqueous media.
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UVA-excited TiO2 generates singlet oxygen, superoxide, and highly reactive hydroxyl radicals.
“UVA-excited TiO 2 has been shown to generate 1 O 2 (189), O 2) and also highly reactive • OH either through reduction of surface hydroxyl group by valence bond holes (190) or by Fenton type reactions (191).”
From Photoinduced Damage to Cellular DNA: Direct and Photosensitized Reactions<sup>†</sup> (2012) · cites this paper as [189]
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- Authors
- Konaka, R., Kasahara, E., Dunlap, W. C., Yamamoto, Y., Chien, K. C., & Inoue, M.
- Affiliations
- Osaka City University (JP)
- Australian Institute of Marine Science (AU)
- The University of Tokyo (JP)
- Venue
- Redox Report
- Publisher
- Informa UK Limited
- Published
- 2001-10
- Volume
- 6
- Issue
- 5
- Pages
- 319-325
- ISSN
- 1351-0002 (ISSN-L)
- 1743-2928
- OpenAlex
- W2026820600
- Cited by
- 89
- References
- 25
- Citations by year
- 2026: 1 · 2025: 4 · 2024: 3 · 2023: 4 · 2022: 4 · 2021: 4 · 2020: 2 · 2019: 1 · 2018: 2 · 2017: 5 · 2016: 3 · 2015: 4 · 2014: 3 · 2013: 4 · 2012: 6
- FWCI
- 1.11
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Locations
- Redox Report (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › TiO2 Photocatalysis and Solar Cells
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Advanced Photocatalysis Techniques
- Physical Sciences › Environmental Science › Water Science and Technology › Advanced oxidation water treatment
- Keywords
- titanium dioxide, singlet oxygen, UV irradiation, aqueous suspensions, reactive oxygen species, superoxide, hydroxyl radicals, DMPO spin adducts, electron spin resonance, photochemistry, kinetic analysis, sodium azide, heavy water
- MeSH terms
- Antioxidants, Cyclic N-Oxides, Electron Spin Resonance Spectroscopy, Hydrogen Peroxide, Piperidones, Spin Labels, Superoxides, Titanium, Ultraviolet Rays, Photosensitizing Agents, Reactive Oxygen Species, Spin Trapping
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