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

Mithun Roy, Shanta Dhar, Basudev Maity, Akhil R. Chakravarty

Research output: Contribution to journalArticle

13 Scopus citations

Abstract

Ferromagnetic dicopper(II) complexes [Cu2(μ-O 2CCH3)(μ-OH)(L)2(μ-L1)] (PF6)2, where L = 1,10-phenanthroline (phen), L 1 = H2O in 1 and L = dipyrido[3,2-d:2′,3′-f] quinoxaline (dpq), L1 = CH3CN in 2, are prepared and structurally characterized. Crystals of 1 and 2 belong to the monoclinic space group of P21/n and P21/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·· ·Cu distances are 3.034 and 3.046 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)](PF 6) (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.

Original languageEnglish (US)
Pages (from-to)173-180
Number of pages8
JournalInorganica Chimica Acta
Volume375
Issue number1
DOIs
StatePublished - Sep 1 2011
Externally publishedYes

Keywords

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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