title: Unique ligand-based oxidative DNA cleavage by zinc(II) complexes of hpyramol and hpyrimol.
abstract: The zinc(II) complexes reported here have been synthesised from the ligand 4-methyl-2-N-(2-pyridylmethyl)aminophenol (Hpyramol) with chloride or acetate counterions. All the five complexes have been structurally characterised, and the crystal structures reveal that the ligand Hpyramol gradually undergoes an oxidative dehydrogenation to form the ligand 4-methyl-2-N-(2-pyridylmethylene)aminophenol (Hpyrimol), upon coordination to Zn(II). All the five complexes cleave the phiX174 phage DNA oxidatively and the complexes with fully dehydrogenated pyrimol ligands were found to be more efficient than the complexes with non-dehydrogenated Hpyramol ligands. The DNA cleavage is suggested to be ligand-based, whereas the pure ligands alone do not cleave DNA. The DNA cleavage is strongly suggested to be oxidative, possibly due to the involvement of a non-diffusible phenoxyl radical mechanism. The enzymatic religation experiments and DNA cleavage in the presence of different radical scavengers further support the oxidative DNA cleavage by the zinc(II) complexes.
authors: Gorlaeus Laboratories, Leiden University, 2300 RA Leiden, The Netherlands.
authors: Palanisamy Uma
authors: PU
authors: Maheswari
authors: Sharief
authors: S
authors: Barends
authors: Seniz
authors: S
authors: Ozalp-Yaman
authors: Paul
authors: P
authors: de Hoog
authors: Hélène
authors: H
authors: Casellas
authors: Simon J
authors: SJ
authors: Teat
authors: Chiara
authors: C
authors: Massera
authors: Martin
authors: M
authors: Lutz
authors: Anthony L
authors: AL
authors: Spek
authors: Gilles P
authors: GP
authors: van Wezel
authors: Patrick
authors: P
authors: Gamez
authors: Jan
authors: J
authors: Reedijk
mesh_terms: D000085:Acetates / Q000737:chemistry; D000627:Aminophenols / Q000737:chemistry*; D010584:Bacteriophage phi X 174 / Q000737:chemistry / Q000378:metabolism; D002413:Cations, Divalent; D002712:Chlorides / Q000737:chemistry; D018360:Crystallography, X-Ray; D004247:DNA / Q000737:chemistry* / Q000378:metabolism; D053837:DNA Cleavage; D004563:Electrochemistry; D016166:Free Radical Scavengers / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D008024:Ligands; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction; D010636:Phenols / Q000737:chemistry; D015032:Zinc / Q000737:chemistry*
chemical_list: D000085:Acetates; D000627:Aminophenols; D002413:Cations, Divalent; D002712:Chlorides; D016166:Free Radical Scavengers; D008024:Ligands; D009942:Organometallic Compounds; D016877:Oxidants; D010636:Phenols; C042329:phenoxy radical; D006859:Hydrogen; D004247:DNA; D015032:Zinc