title: Oxidative cleavage of DNA by a new ferromagnetic linear trinuclear copper(II) complex in the presence of H2O2/sodium ascorbate.
abstract: A new trinuclear copper(II) complex has been synthesized and structurally characterized: [Cu(3)(L)(2)(HCOO)(2)(OH)(2)](infinity) (HL = (N-pyrid-2-ylmethyl)benzenesulfonylamide). In the complex, the central copper ion is six-coordinated. The coordination spheres of the terminal copper atoms are square pyramidal, the apical positions being occupied by a sulfonamido oxygen of the contiguous trimer. As a consequence, the complex can be considered a chain of trinuclear species. The three copper atoms are in a strict linear arrangement, and adjacent coppers are connected by a hydroxo bridge and a bidentate syn-syn carboxylato group. The mixed bridging by a hydroxide oxygen atom and a bidentate formato group leads to a noncoplanarity of the adjacent basal coordination planes with a dihedral angle of 61.4(2) degrees. Susceptibility measurements (2-300 K) reveal a strong ferromagnetic coupling, J = 79 cm(-1), leading to a quartet ground state that is confirmed by the EPR spectrum. The ferromagnetic coupling arises from the countercomplementarity of the hydroxo and formato bridges. The trinuclear complex cleaves DNA efficiently, in the presence of hydrogen peroxide/sodium ascorbate. tert-Butyl alcohol and sodium azide inhibit the oxidative cleavage, suggesting that the hydroxyl radical and singlet oxygen are involved in the DNA degradation.
authors.affiliation: Departamento de Química Inorgánica, Universidad de Valencia, Avda. Vicent Andrés Estellés, s/n, 46100 Burjassot, Spain.
authors.forename: M
authors.initials: M
authors.lastname: González-Alvarez
authors.forename: G
authors.initials: G
authors.lastname: Alzuet
authors.forename: J
authors.initials: J
authors.lastname: Borrás
authors.forename: B
authors.initials: B
authors.lastname: Macías
authors.forename: A
authors.initials: A
authors.lastname: Castiñeiras
mesh_terms: D000465:Algorithms; D001205:Ascorbic Acid / Q000031:analogs & derivatives / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004247:DNA / Q000737:chemistry* / Q000187:drug effects*; D004578:Electron Spin Resonance Spectroscopy; D004587:Electrophoresis, Agar Gel; D006861:Hydrogen Peroxide / Q000737:chemistry; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010084:Oxidation-Reduction; D010957:Plasmids / Q000737:chemistry
chemical_list: D009942:Organometallic Compounds; D003300:Copper; D004247:DNA; D006861:Hydrogen Peroxide; D001205:Ascorbic Acid