title: Photoinduced DNA Interstrand Cross-Link Formation by Naphthalene Boronates via a Carbocation.
abstract: Most photoinduced DNA cross-link formation by a bifunctional aryl derivative is through a bisquinone methide. DNA cross-linking via a bisarylcarbocation remains a less explored area. We designed and synthesized a series of naphthalene boronates that produce DNA interstrand cross-links via a carbocation upon UV irradiation. A free radical was generated from the naphthalene boronates with 350 nm irradiation and further converted to a carbocation by electron transfer. The activation mechanism was determined using the orthogonal traps, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and methoxyamine that react with either the free radical or the carbocation but not both. This represents a novel example of photoinduced DNA cross-link formation via carbocations generated from a bisaryl derivative. This work provides information useful for the design of novel photoactivated DNA cross-linking agents.
authors.affiliation: Department of Chemistry and Biochemistry, University of Wisconsin Milwaukee, 3210 N. Cramer St., Milwaukee, WI, 53211, USA.
authors.forename: Yibin
authors.initials: Y
authors.lastname: Wang
authors.affiliation: Department of Chemistry and Biochemistry, University of Wisconsin Milwaukee, 3210 N. Cramer St., Milwaukee, WI, 53211, USA.
authors.forename: Zechao
authors.initials: Z
authors.lastname: Lin
authors.affiliation: Department of Chemistry and Biochemistry, University of Wisconsin Milwaukee, 3210 N. Cramer St., Milwaukee, WI, 53211, USA.
authors.forename: Heli
authors.initials: H
authors.lastname: Fan
authors.affiliation: Department of Chemistry and Biochemistry, University of Wisconsin Milwaukee, 3210 N. Cramer St., Milwaukee, WI, 53211, USA. pengx@uwm.edu.
authors.forename: Xiaohua
authors.initials: X
authors.lastname: Peng
mesh_terms: D001897:Boronic Acids / Q000737:chemistry*; D003432:Cross-Linking Reagents / Q000737:chemistry*; D003497:Cyclic N-Oxides / Q000737:chemistry; D004247:DNA / Q000737:chemistry*; D004249:DNA Damage; D004579:Electron Transport; D005609:Free Radicals / Q000737:chemistry; D006898:Hydroxylamines / Q000737:chemistry; D009281:Naphthalenes / Q000737:chemistry*; D009690:Nucleic Acid Conformation; D055668:Photochemical Processes; D014466:Ultraviolet Rays
chemical_list: D001897:Boronic Acids; D003432:Cross-Linking Reagents; D003497:Cyclic N-Oxides; D005609:Free Radicals; D006898:Hydroxylamines; D009281:Naphthalenes; D004247:DNA; C005214:methoxyamine; C003959:TEMPO
keywords: DNA cross-linking; carbocations; naphthalene boronates; photoactivation; photochemistry; radicals