title: Investigation of metal-oligonucleotide complexes by nanoelectrospray tandem mass spectrometry in the positive mode.
abstract: The formation and fragmentation of multiply metal-coordinated oligonucleotides was studied by nanoelectrospray tandem mass spectrometry in the positive ion mode. Fundamental aspects of the gas-phase behavior of metal-oligonucleotide complexes are revealed. The addition of transition metal ions, such as iron(II), iron(III), and zinc(II), leads to very stable metal-oligonucleotide complexes which show heavily altered fragmentation patterns in contrast to uncomplexed oligonucleotides. The site of metal ion complexation was located by collision-induced dissociation (CID) experiments. It was found that all three metal ions investigated predominantly coordinate to the central phosphate groups of the oligonucleotides. Furthermore, it is demonstrated that the fragmentation of such complexes depends highly upon the metal ion complexed as well as on the sequence of the nucleobases in the oligonucleotide.
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern, CH-3012 Bern, Switzerland.
authors.forename: Selina T M
authors.initials: ST
authors.lastname: Monn
authors.forename: Stefan
authors.initials: S
authors.lastname: Schürch
mesh_terms: D008670:Metals / Q000032:analysis*; D036103:Nanotechnology; D009841:Oligonucleotides / Q000032:analysis*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods
chemical_list: D008670:Metals; D009841:Oligonucleotides
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