title: DNA cleavage by the photolysis of cyclopentadienyl metal complexes: mechanistic studies and sequence selectivity of strand scission by CpW(CO)3CH3.
abstract: [Reaction: see text]. The photolysis of CpW(CO)3Me has been shown to produce methyl radicals and to cleave DNA in a single-stranded manner, and preliminary evidence implicated a carbon-centered radical in this process. In this work, the mechanism of strand scission in this reaction was determined to occur by hydrogen atom abstraction from the 4'- and 5'-positions of the deoxyribose moiety of the backbone of DNA. Additionally, in a side reaction that does not lead to frank strand scission, all four bases of DNA are methylated under these conditions; however, none of these base or backbone modifications lead to the formation of abasic sites.
authors.affiliation: Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA. mohlerdl@jmv.edu
authors.forename: Debra L
authors.initials: DL
authors.lastname: Mohler
authors.forename: Jennifer R
authors.initials: JR
authors.lastname: Downs
authors.forename: Allison L
authors.initials: AL
authors.lastname: Hurley-Predecki
authors.forename: Jennifer R
authors.initials: JR
authors.lastname: Sallman
authors.forename: Peter M
authors.initials: PM
authors.lastname: Gannett
authors.forename: Xianglin
authors.initials: X
authors.lastname: Shi
mesh_terms: D003517:Cyclopentanes / Q000737:chemistry*; D004247:DNA / Q000737:chemistry / Q000528:radiation effects*; D019175:DNA Methylation; D003855:Deoxyribose / Q000737:chemistry / Q000378:metabolism; D004578:Electron Spin Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*; D010777:Photochemistry; D010782:Photolysis; D010957:Plasmids; D014414:Tungsten / Q000737:chemistry*
chemical_list: D003517:Cyclopentanes; D009942:Organometallic Compounds; D003855:Deoxyribose; D004247:DNA; D014414:Tungsten