Triplet Formation of 4-Thiothymidine and Its Photosensitization to Oxygen Studied by Time-Resolved Thermal Lensing Technique
Abstract
Excited-state dynamics of 4-thiothymidine (S4-TdR) and its photosensitization to molecular oxygen in solution with UVA irradiation were investigated. Absorption and emission spectra measurements revealed that UVA photolysis of S4-TdR gives rise to a population of T1(pipi*), following S2(pipi*) --> S1(npi*) internal conversion. In transient absorption measurement, the 355 nm laser photolysis gave broad absorption (380-600 nm) bands of triplet S4-TdR. The time-resolved thermal lensing (TRTL) signal of S4-TdR containing the thermal component due to decay of triplet S4-TdR was clearly observed by the 355 nm laser excitation. The quantum yield for S1 --> T1 intersystem crossing was estimated to be unity by a triplet quenching experiment with potassium iodide. In the presence of molecular oxygen, the photosensitization from triplet S4-TdR gave rise to singlet oxygen O2 (1Deltag) with a quantum yield of 0.50. Therapeutic implications of such singlet oxygen formation are discussed.
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High phototoxicity is rationalized by oxygen-independent formation of DNA photoproducts including S5 thietane derivative, a 6-4PP analogue, through photocycloaddition with vicinal thymine and putative ICLs.
“This was rationalized in terms of oxygenindependent formation of DNA photoproducts including an expected S5 thietane derivative, a 6-4PP analogue (227), through photocycloaddition with vicinal thymine and putative ICLs (228) that however remain to be characterized.”
From Photoinduced Damage to Cellular DNA: Direct and Photosensitized Reactions<sup>†</sup> (2012) · cites this paper as [228]
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Quantum effects in photosensitization: the case of singlet oxygen generation by thiothymines
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Excited state properties of 5‐fluoro ‐4‐thiouridine derivative†
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- Authors
- Harada, Y., Suzuki, T., Ichimura, T., & Xu, Y.-Z.
- Affiliations
- Tokyo Institute of Technology (JP)
- Corresponding author
- Suzuki, Tadashi
- Venue
- The Journal of Physical Chemistry B
- Publisher
- American Chemical Society (ACS)
- Published
- 2007-04-18
- Volume
- 111
- Issue
- 19
- Pages
- 5518-5524
- ISSN
- 1520-5207 (ISSN-L)
- 1520-6106
- OpenAlex
- W2072509880
- Cited by
- 90
- References
- 29
- Citations by year
- 2026: 4 · 2025: 4 · 2024: 5 · 2023: 3 · 2022: 4 · 2021: 7 · 2020: 8 · 2019: 7 · 2018: 6 · 2017: 8 · 2016: 4 · 2015: 2 · 2014: 7 · 2013: 3 · 2012: 2
- FWCI
- 1.96
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- The Journal of Physical Chemistry B (publishedVersion)
- PubMed (publishedVersion)
- Open Research Online (The Open University) (submittedVersion)
- Topics
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
- Health Sciences › Medicine › Pulmonary and Respiratory Medicine › Photodynamic Therapy Research Studies
- Physical Sciences › Materials Science › Materials Chemistry › Luminescence and Fluorescent Materials
- Keywords
- 4-thiothymidine, triplet formation, intersystem crossing, singlet oxygen, photosensitization, excited-state dynamics, triplet quenching, potassium iodide, transient absorption spectroscopy, quantum yield
- MeSH terms
- Hot Temperature, Oxygen, Photochemistry, Thymidine, Time Factors, Molecular Structure
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