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Modification of Guanine with Photolabile N ‐Hydroxypyridine‐2(1 H )‐thione: Monomer Synthesis, Oligonucleotide Elaboration, and Photochemical Studies
Author(s) -
Vrantza Despoina,
Kaloudis Panagiotis,
Leondiadis Leondios,
Gimisis Thanasis,
Vougioukalakis Georgios C.,
Orfanopoulos Michael,
Gasparutto Didier,
Cadet Jean,
Encinas Susana,
Paris Cecilia,
Miranda Miguel A.
Publication year - 2006
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200690220
Subject(s) - chemistry , photochemistry , deoxyguanosine , singlet oxygen , oligonucleotide , sulfanyl , guanine , triplet state , monomer , guanosine , oxygen , stereochemistry , dna , organic chemistry , molecule , adduct , nucleotide , biochemistry , gene , polymer
The photochemistry of N ‐hydroxypyridine‐2(1 H )‐thione (NHPT), inserted as a photolabile modifier at the 6‐position of 2′‐deoxyguanosine or guanosine, has been evaluated. In particular, 6‐[(1‐oxidopyridin‐2‐yl)sulfanyl]‐ ( 1a ) and 6‐[(pyridin‐2‐yl)sulfanyl]‐2′,6‐dideoxyguanosine ( 2a ), novel photolabile derivatives of the natural nucleosides, were synthesized and characterized. The observed photolysis products of 1a in organic solvents could only be rationalized by assuming a rapid equilibrium with the corresponding 6‐[(2‐thioxopyridin‐1(2 H )‐yl)oxy] analogue 3a ( Scheme 5 ). Transient spectroscopy of 1a indicated a strong triplet‐excited state suitable for triplet → triplet energy transfer or singlet‐oxygen generation. The NHPT function was stable enough for (slightly modified) automated solid‐phase oligonucleotide synthesis. The utility of the above compounds is discussed, as well as their potential use in photosensitization of reactive oxygen species in DNA.