Hole Migration In Telomere-Based Oligonucleotide Anions And G-Quadruplexes

Wen Li, Edita Mjekiqi, Wessel Douma, Xin Wang, Oksana Kavatsyuk, Ronnie Hoekstra, Jean-Christophe Poully, Thomas Schlathölter*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

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Abstract

Vacuum ultraviolet photoionization of a gas-phase oligonucleotide anion leads to the formation of a valence hole. This hole migrates towards an energetically favorable site where it can weaken bonds and ultimately lead to bond cleavage. We have studied VUV photoionization of deprotonated oligonucleotides containing the human telomere sequence dTTAGGG and G-quadruplex structures consisting of four dTGGGGT single strands, stabilized by NH4+ counter ions. The oligonucleotide and G-quadruplex anions were confined in a radiofrequency ion trap, interfaced with a synchrotron beamline and the photofragmentation was studied using time-of-flight mass spectrometry. Oligonucleotide 12-mers containing the 5´-TTAGGG sequence were found to predominantly break in the GGG region, whereas no selective bond cleavage region was observed for the reversed 5´-GGGATT sequence. For G-quadruplex structures, fragmentation was quenched and mostly non-dissociative single and double electron removal was observed.
Original languageEnglish
Pages (from-to)16114 –16119
Number of pages6
JournalChemistry - A European Journal
Volume25
Issue number70
DOIs
Publication statusPublished - 15-Oct-2019

Keywords

  • Charge migration
  • oligonucleotide
  • photoionization
  • synchrotron radiation
  • telomere
  • STRAND BREAKS
  • DNA
  • SPECTROSCOPY
  • PHOTOIONIZATION
  • THERAPEUTICS
  • DUPLEX
  • CANCER

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