Intermolecular vs. intramolecular photoinduced electron transfer from nucleotides in DNA to acridinium ion derivatives in relation with DNA cleavage

Makiko Tanaka, Kazusa Yukimoto, Kei Ohkubo, Shunichi Fukuzumi

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

Photoirradiation of various 10-methylacridinium ions (AcrR+, R = H, iPr, and Ph) intercalated in DNA results in ultrafast intramolecular electron transfer, followed by rapid back electron transfer between AcrR+ and nucleotides in DNA. The electron-transfer dynamics in DNA were monitored by femtosecond time-resolved transient absorption spectroscopy. Both acridinyl radical and nucleotide radical cations, formed in the photoinduced electron transfer in DNA, were successfully detected in an aqueous solution. These transient absorption spectra were assigned by the comparison with those of DNA nucleotide radical cations, which were obtained by the intermolecular electron-transfer oxidation of nucleotides with the electron-transfer state of 9-mesityl-10-methylacridinium ion (Acr{radical dot}-Mes{radical dot}+) produced upon photoexcitation of Acr+-Mes. Photoinduced cleavage of DNA with various acridinium ions (AcrR+, R = H, iPr, Ph, and Mes) has also been examined by agarose gel electrophoresis, which indicates that the rapid intramolecular back electron transfer between acridinyl radical and nucleotide radical cation in DNA suppresses the DNA cleavage as compared with the intermolecular electron-transfer oxidation of nucleotides with Acr{radical dot}-Mes{radical dot}+.

Original languageEnglish
Pages (from-to)206-212
Number of pages7
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume197
Issue number2-3
DOIs
StatePublished - 25 Jun 2008

Bibliographical note

Funding Information:
This work was partially supported by a Grant in Aid (Nos. 19205019 and 19750034) from the Ministry of Education, Culture, Sports, Science and Technology, Japan (to S.F. and K.O.), and JSPS Fellowships (to M.T.).

Keywords

  • DNA
  • Electron transfer
  • Laser flash photolysis
  • Nucleotide
  • Radical

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