NDLI: Photochemical reactions of 4-thiouridine disulfide and 4-benzylthiouridine—the involvement of the 4-pyrimidinylthiyl radical

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Photochemical & Photobiological Sciences Vol -6

Photochemical & Photobiological Sciences Vol -5

Photochemical & Photobiological Sciences Vol -4

Photochemical & Photobiological Sciences Vol -3

Photochemical & Photobiological Sciences Vol -2

Photochemical reactions of 4-thiouridine disulfide and 4-benzylthiouridine—the involvement of the 4-pyrimidinylthiyl radical

Content Provider	Royal Society of Chemistry (RSC)
Author	Filipiak, Piotr Marciniak, Bronislaw Taras-Goslinska, Katarzyna Wenska, Grazyna Hug, Gordon L.
Copyright Year	2008
Abstract	The reactions of a disulfide and a benzylsulfide derived from 4-thiouridine were studied in aqueous acetonitrile using stationary and laser flash photolysis methods. Irradiation of the compounds results in specific cleavage of the S–S bond in the disulfide and the S–CH2 bond in the sulfide. Identical pyrimidine-derived intermediates were observed in the transient absorption spectra (λmax = 420 nm, εmax ∼ 2 500 M−1 cm−1) recorded for both compounds in laser flash photolysis experiments. The intermediate was identified as the 4-pyrimidinylthiyl radical. Irradiation of the disulfide in the absence of oxygen gives 4-thiouridine while the sulfide under identical conditions produced, additionally, 3-benzyl-4-thiouridine as a stable photoproduct. The formation of the latter photoproduct provides evidence for the existence of the N-centered 4-thioxopyrimidynyl radical formed from the initially produced S-centered (thiyl) radical. The 4-thiouridine is formed from the radicals generated in the primary photochemical step by an H abstraction reaction from the solvent (acetonitrile) or from additives (alcohols) that were purposely added. Interestingly, in contrast to the benzylsulfide, the photoreaction of the disulfide is quenched by molecular oxygen with the concomitant formation of uridine. However it appears that uridine is not produced as a result of the reaction of the radicals with oxygen. A mechanism is proposed for the photochemical transformations of the disulfide and benzylsulfide derived from 4-thiouridine. The proposed mechanism is based on the structures of the identified stable photoproducts, the values of the photoreaction quantum yields determined under differing irradiation conditions, and the flash photolysis results.
Starting Page	250
Ending Page	256
Page Count	7
File Format	HTM / HTML PDF
ISSN	1474905X
Volume Number	7
Issue Number	2
Journal	Photochemical & Photobiological Sciences
DOI	10.1039/b713218b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Thioether Pyrimidine dimer Quantum Disulfide Acetonitrile Laser Irradiation Covalent bond Uridine Flash photolysis Benzyl group Solvent Nucleophile Photochemistry
Content Type	Text
Resource Type	Article
Subject	Physical and Theoretical Chemistry

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