title: Electron interaction with phosphate cytidine oligomer dCpdC: base-centered radical anions and their electronic spectra.
abstract: Computational chemistry approach was applied to explore the nature of electron attachment to cytosine-rich DNA single strands. An oligomer dinucleoside phosphate deoxycytidylyl-3',5'-deoxycytidine (dCpdC) was selected as a model system for investigations by density functional theory. Electron distribution patterns for the radical anions of dCpdC in aqueous solution were explored. The excess electron may reside on the nucleobase at the 5' position (dC(•-)pdC) or at the 3' position (dCpdC(•-)). From comparison with electron attachment to the cytosine related DNA fragments, the electron affinity for the formation of the cytosine-centered radical anion in DNA is estimated to be around 2.2 eV. Electron attachment to cytosine sites in DNA single strands might cause perturbations of local structural characteristics. Visible absorption spectroscopy may be applied to validate computational results and determine experimentally the existence of the base-centered radical anion. The time-dependent DFT study shows the absorption around 550-600 nm for the cytosine-centered radical anions of DNA oligomers. This indicates that if such species are detected experimentally they would be characterized by a distinctive color.
authors.affiliation: Drug Design & Discovery Center, State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences , Shanghai 201203 China.
authors.forename: Jiande
authors.initials: J
authors.lastname: Gu
authors.forename: Jing
authors.initials: J
authors.lastname: Wang
authors.forename: Jerzy
authors.initials: J
authors.lastname: Leszczynski
mesh_terms: D000838:Anions / Q000737:chemistry; D003841:Deoxycytidine / Q000031:analogs & derivatives* / Q000737:chemistry*; D015226:Dinucleoside Phosphates / Q000737:chemistry*; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry; D015394:Molecular Structure; D011789:Quantum Theory; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000838:Anions; D015226:Dinucleoside Phosphates; D005609:Free Radicals; D003841:Deoxycytidine