4.5 Article

Dicopper(II) complexes showing DNA hydrolase activity and monomeric adduct formation with bis(4-nitrophenyl)phosphate

期刊

INORGANICA CHIMICA ACTA
卷 375, 期 1, 页码 173-180

出版社

ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2011.04.046

关键词

Copper; Hydrolytic DNA cleavage; Phenanthroline bases; Crystal structures; Bis(4-nitrophenyl)phosphate adduct; Reaction kinetics

资金

  1. Department of Science and Technology (DST), Government of India [SR/S5/MBD-02/2007]
  2. DST

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Ferromagnetic dicopper(II) complexes [Cu-2(mu-O2CCH3)(mu-OH)(L)(2)(mu-L-1)](PF6)(2), where L = 1,10-phenanthroline (phen), L-1 = H2O in 1 and L = dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), L-1 = CH3CN in 2, are prepared and structurally characterized. Crystals of 1 and 2 belong to the monoclinic space group of P2(1)/n and P2(1)/m, respectively. The copper(II) centers display distorted square-pyramidal geometry having a phenanthroline base and two oxygen atoms of the bridging hydroxo and acetate group in the basal plane. The fifth coordination site has weak axially bound bridging solvent molecule H2O in 1 and CH3CN in 2. The Cu center dot center dot center dot Cu distances are 3.034 and 3.046 angstrom in 1 and 2, respectively. The complexes show efficient hydrolytic cleavage of supercoiled pUC19 DNA as evidenced from the mechanistic studies that include T4 DNA ligase experiments. The binuclear complexes form monomeric copper(II) adducts [Cu(L)(2)(BNPP)](PF6) (L = phen, 3; dpq, 4) with bis(4-nitrophenyl)phosphate (BNPP) as a model phosphodiester. The crystal structures of 3 and 4 reveal distorted trigonal bipyramidal geometry in which BNPP binds through the oxygen atom of the phosphate. The kinetic data of the DNA cleavage reactions of the binuclear complexes under pseudo- and true-Michaelis-Menten conditions indicate remarkable enhancement in the DNA hydrolysis rate in comparison to the control data. (C) 2011 Elsevier B.V. All rights reserved.

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