Gas-phase formation of radical cations of monomers and dimers of guanosine by collision-induced dissociation of Cu(II)-guanosine complexes.
An electrosprayed water/methanol solution of guanosine and Cu(NO3)2 was observed to give rise to gas-phase copper complexed ions of [CuLn]*2+, [CuL(MeOH)n]*2+, and [CuG n(NO3)]*+, as well as the ions [L]*+, [L+H]+, [G]*+, and [G+H]+ (L=guanosine, G=guanine). The Collision-Induced Dissociation (CID) of [CuL3]*2+ and [CuL(MeOH)n]*2+ (n=2, 3) generates guanosine radical cations [L]*+, while dimeric guanosine radical cations [L2]*+ are generated in the dissociation of [CuL4]*2+. Protonated guanosine [L+H]+ is one of the main products in the primary dissociation of [CuL2]*2+, while the dissociation of the higher-order [CuG2]*2+ produces the [G]*+ radical cation. The guanosine dimer radical cation, [L2]*+ presumably arises from the interaction of two guanosine molecules via proton and hydrogen bonding and is observed to dissociate into [L+H]+ and [L-H]* at low energies. We propose that the first two ligands bind strongly with Cu(II) through N7 and O6 to form a [CuL2]*2+ complex with a four-coordinated planar structure and that a third ligand binds loosely with copper to form [CuL3]*2+. Additional ligation observed in the formation of [CuLn]*2+ (n<or=6) ions is presumed to occur by hydrogen bonding. The ribose group of guanosine appears to play an important role in the stabilization of the doubly charged Cu-guanosine complex and in intraligand proton transfer upon CID. The molecular radical cations [L]*+ observed in the ESI-MS spectrum at low declustering potentials originate primarily from [CuL(MeOH)2,3]*2+ complexes which can dissociate more easily than [CuL3]*2+.
Cheng
Ping
P
Department of Chemistry, Centre for Research in Mass Spectrometry and Centre for Research in Earth and Space Science, York University, Toronto, Ontario, Canada, M3J 1P3.
Bohme
Diethard K
DK
D002412:Cations; D003300:Copper / Q000737:chemistry*; D019281:Dimerization; D005740:Gases / Q000737:chemistry; D006151:Guanosine / Q000737:chemistry*; D008024:Ligands; D000432:Methanol / Q000737:chemistry; D009566:Nitrates / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D014867:Water / Q000737:chemistry
D002412:Cations; D005740:Gases; D008024:Ligands; D009566:Nitrates; D014867:Water; D006151:Guanosine; D003300:Copper; C516433:copper(II) nitrate; D000432:Methanol