We have studied soft X-ray photoabsorption in the doubly deprotonated gas-phase oligonucleotide [dTGGGGT-2H]^2-. The dominating decay mechanism of the X-ray induced inner shell vacancy was found to be Auger decay...

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 Vacuum UV 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.