Cytosine Radical Cations: A Gas-Phase Study Combining IRMPD Spectroscopy, UVPD Spectroscopy, Ion-Molecule Reactions, and Theoretical Calculations
Status PubMed-not-MEDLINE Jazyk angličtina Země Německo Médium print-electronic
Typ dokumentu časopisecké články
PubMed
28319295
DOI
10.1002/cphc.201700281
Knihovny.cz E-zdroje
- Klíčová slova
- IRMPD spectroscopy, UVPD spectroscopy, ion-molecule reactions, nucleobases, radical ions,
- Publikační typ
- časopisecké články MeSH
The radical cation of cytosine (Cyt.+ ) is generated by dissociative oxidation from a ternary CuII complex in the gas phase. The radical cation is characterized by infrared multiple photon dissociation (IRMPD) spectroscopy in the fingerprint region, UV/Vis photodissociation (UVPD) spectroscopy, ion-molecule reactions, and theoretical calculations (density functional theory and ab initio). The experimental IRMPD spectrum features diagnostic bands for two enol-amino and two keto-amino tautomers of Cyt.+ that are calculated to be among the lowest energy isomers, in agreement with a previous study. Although the UVPD action spectrum can also be matched to a combination of the four lowest energy tautomers, the presence of a nonclassical distonic radical cation cannot be ruled out. Its formation is, however, unlikely due to the high energy of this isomer and the respective ternary CuII complex. Gas-phase ion-molecule reactions showed that Cyt.+ undergoes hydrogen-atom abstraction from 1-propanethiol, radical recombination reactions with nitric oxide, and electron transfer from dimethyl disulfide.
Department of Chemistry and Biochemistry Northern Illinois University DeKalb IL 60115 USA
Department of Chemistry University of Washington Bagley Hall Box 351700 Seattle Washington 98195 USA
Laboratoire de Chimie Physique Université Paris Sud UMR8000 CNRS 91405 Orsay France
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