title: Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions.
abstract: Multiply deprotonated hexadeoxyadenylate anions, (A6-nH)(n-), where n = 3-5, have been subjected to reaction with a range of divalent transition-metal complex cations in the gas phase. The cations studied included the bis- and tris-1,10-phenanthroline complexes of CuII, FeII, and CoII, as well as the tris-1,10-phenanthroline complex of RuII. In addition, the hexadeoxyadenylate anions were subjected to reaction with the singly charged FeIII and CoIIIN,N'-ethylenebis(salicylideneiminato) complexes. The major competing reaction channels are electron-transfer from the oligodeoxynucleotide anion to the cation, the formation of a complex between the anion and cation, and the incorporation of the transition-metal into the oligodeoxynucleotide. The latter process proceeds via the anion/cation complex and involves displacement of the ligand(s) in the transition-metal complex by the oligodeoxynucleotide. Competition between the various reaction channels is governed by the identity of the transition-metal cation, the coordination environment of the metal complex, and the oligodeoxynucleotide charge state. In the case of the divalent metal phenanthroline complexes, competition between electron-transfer and metal ion incorporation is particularly sensitive to the coordination number of the reagent metal complexes. Both electron-transfer and metal ion incorporation occur to significant extents with the bis-phenanthroline ions, whereas the tris-phenanthroline ions react predominantly by metal ion incorporation. To our knowledge this work reports the first observations of the gas-phase incorporation of multivalent transition-metal cations into oligodeoxynucleotide anions and represents a means for the selective incorporation of transition-metal counter-ions into gaseous oligodeoxynucleotides.
authors: School of Chemistry, University of Melbourne, Melbourne, Australia.
authors: Christopher K
authors: CK
authors: Barlow
authors: Brittany D M
authors: BD
authors: Hodges
authors: Yu
authors: Y
authors: Xia
authors: Richard A J
authors: RA
authors: O'Hair
authors: Scott A
authors: SA
authors: McLuckey
mesh_terms: D000838:Anions / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D005029:Ethylenediamines / Q000737:chemistry; D005740:Gases; D007501:Iron / Q000737:chemistry; D008670:Metals / Q000737:chemistry*; D008956:Models, Chemical; D009838:Oligodeoxyribonucleotides / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods*
chemical_list: D000838:Anions; D005029:Ethylenediamines; D005740:Gases; D008670:Metals; D009838:Oligodeoxyribonucleotides; D003035:Cobalt; D003300:Copper; D012428:Ruthenium; C011452:disalicylaldehyde ethylenediamine; D007501:Iron