Charge state effect on the zwitterion influence on stability of non-covalent interaction of single-stranded DNA with peptides

Sandra Alves, Amina Woods, Jean Claude Tabet

Research output: Contribution to journalArticlepeer-review

19 Scopus citations


Negative ion ESI mass spectrometry was used to study the gas-phase stability and dissociation pathways of peptide-DNA complexes. We show that bradykinin and three modified peptides containing the basic residue arginine or lysine form stable interactions with single-stranded oligonucleotides. ESI-MS/MS of complexes of T8 with PPGFSPFRR resulted in a major dissociation pathway through cleavage of the peptide covalent bond. The stability of the complex is due to electrostatic interaction between the negatively charged phosphate group and the basic side chain of the arginine and lysine residues as demonstrated by Vertes et al. and Woods et al. In fact, the present work establishes the role played by zwitterions on complex stabilisation. The presence of protons in nucleobase and/or amino acid contributes in reinforcing the strength of the salt bridge (SB) interaction. The zwitterionic form of the most basic of amino acid residues, arginine, is assumed to form a strong SB interaction to the negatively charged phosphate groups of DNA. This non-covalent complex is stable enough to withstand disruption of the non-covalent interaction and to first break the covalent bond. Moreover, the dependence of fragmentation patterns upon the complex charge state is explained by the fact that the net number of negative charges modulates the number of zwitterionic sites, which stabilise the complexes. Finally, the weak influence of the nucleobase is assumed by the existence of competition for proton addition between the nucleobase and the R/K side chain leading to a decrease in the stabilisation of the SB interaction.

Original languageEnglish (US)
Pages (from-to)1613-1622
Number of pages10
JournalJournal of Mass Spectrometry
Issue number12
StatePublished - Dec 2007
Externally publishedYes


  • ESI mass spectrometry
  • Noncovalent complexes
  • Salt bridge interaction

ASJC Scopus subject areas

  • Organic Chemistry
  • Spectroscopy
  • Biophysics


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