Geometric effect on the photocrosslinking reaction between 3-cyanovinylcarbazole nucleoside and pyrimidine base in DNA/RNA heteroduplex

Photochem Photobiol. 2013 Sep-Oct;89(5):1095-9. doi: 10.1111/php.12118. Epub 2013 Jul 29.


To clarify the geometric effect of the ultra-fast photocrosslinking reaction of photoreactive oligodeoxyribonucleotide containing 3-cyanovinylcarbazole nucleoside ((CNV)K) on uridine in complementary RNA strands, pseudouridine (Ψ), which is an isomer of uridine with a C5-C1' glycosidic bond, was introduced to the photocrosslink site of (CNV)K in complementary RNA instead of U. The photoreactivity of (CNV)K toward Ψ was two-fold lower than that of U, suggesting that the geometry between the vinyl moiety on (CNV)K and the reactive double bond in the pyrimidine base has a large affect on the photoreactivity of (CNV)K. Contrary to the case of U, the reactivity of the (CNV)K toward Ψ was decreased by the decrease of reaction temperature below the Tm of heteroduplex, suggesting that the flexible structure of the duplex is advantageous for the photocrosslinking reaction with Ψ, whose reactive double bond possesses unfavorable geometry for the photocrosslinking reaction with (CNV)K. These basic findings might contribute to the development of a geometry selective photocrosslinking reaction. This is the first example of a sequence specific photocrosslinking reaction toward Ψ, which is the most abundant posttranscriptionally modified nucleoside.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbazoles / chemistry*
  • Chromatography, High Pressure Liquid
  • Electrophoresis, Polyacrylamide Gel
  • Nucleic Acid Heteroduplexes*
  • Nucleosides / chemistry*
  • Photochemical Processes*
  • Pyrimidines / chemistry*


  • Carbazoles
  • Nucleic Acid Heteroduplexes
  • Nucleosides
  • Pyrimidines
  • pyrimidine