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Photoswitchable Formation of a DNA Interstrand Cross‐Link by a Coumarin‐Modified Nucleotide
Author(s) -
Haque Mohammad Mojibul,
Sun Huabing,
Liu Shuo,
Wang Yinsheng,
Peng Xiaohua
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201310609
Subject(s) - chemistry , pyrimidine , nucleoside , deoxyadenosine , cycloaddition , adduct , nucleotide , thymidine , nucleoside analogue , reactivity (psychology) , dna , coumarin , stereochemistry , photochemistry , catalysis , organic chemistry , biochemistry , medicine , alternative medicine , pathology , gene
A coumarin‐modified pyrimidine nucleoside ( 1 ) has been synthesized using a Cu I ‐catalyzed click reaction and incorporated into oligodeoxynucleotides (ODNs). Interstrand cross‐links are produced upon irradiation of ODNs containing 1 at 350 nm. Cross‐linking occurs through a [2+2] cycloaddition reaction with the opposing thymidine, 2′‐deoxycytidine, or 2′‐deoxyadenosine. A much higher reactivity was observed with dT than dC or dA. Irradiation of the dT‐ 1 and dC‐ 1 cross‐linked products at 254 nm leads to a reversible ring‐opening reaction, while such phenomena were not observed with dA‐ 1 adducts. The reversible reaction is ultrafast and complete within 50–90 s. Consistent photoswitching behavior was observed over 6 cycles of irradiation at 350 nm and 254 nm. To the best of our knowledge, this is the first example of photoswitchable interstrand cross‐linking formation induced by a modified pyrimidine nucleoside.