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Synthesis, structure, DNA binding and DNA cleavage activity of oxovanadium(IV) N-salicylidene-S-methyldithiocarbazate complexes of phenanthroline bases

Sasmal, Pijus K and Patra, Ashis K and Chakravarty, Akhil R (2008) Synthesis, structure, DNA binding and DNA cleavage activity of oxovanadium(IV) N-salicylidene-S-methyldithiocarbazate complexes of phenanthroline bases. In: Journal of Inorganic Biochemistry, 102 (7). pp. 1463-1472.

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Abstract

Ternary oxovanadium(IV) complexes [VO(salmdtc)(B)] (1–3), where salmdtc is dianionic N-salicylidene-S-methyldithiocarbazate and B is N,N-donor phenanthroline bases like 1,10-phenanthroline (phen, 1), dipyrido[3,2-d:2,3-f ]quinoxaline (dpq, 2) and dipyrido[3,2-a:20,30-c]phenazine (dppz, 3), are prepared, characterized and their DNA binding and DNA cleavage activity studied. Complex 3 is structurally characterized by single-crystal X-ray crystallography. The molecular structure shows the presence of a vanadyl group in six-coordinate $VN_3O_2S$ coordination geometry. The S-methyldithiocarbazate Schiff base acts as a tridentate NSO-donor ligand in a meridional binding mode. The N,N-donor heterocyclic base displays a chelating mode of binding with an N-donor site trans to the vanadyl oxo-group. The complexes show a d–d band in the range of 675–707 nm in DMF. They exhibit an irreversible oxidative cyclic voltammetric response near 0.9 V due to the V(V)/V(IV) couple and a quasi-reversible reductive V(IV)/V(III) redox couple near -1.0 V vs. SCE in DMF-0.1 M TBAP. The complexes show good binding propensity to calf thymus DNA giving binding constant values in the range of $7.4 \times10^4 -2.3 \times 10^5 M^{-1}$. The thermal denaturation and viscosity binding data suggest DNA surface and/or groove binding nature of the complexes. The complexes show poor chemical nuclease activity in dark in the presence of 3-mercaptopropionic acid (MPA) or hydrogen peroxide. The dpq and dppz complexes show efficient DNA cleavage activity in UV-A light of 365 nm via a type-II mechanistic pathway involving formation of singlet oxygen $(^1O_2)$ as the reactive species.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Elsevier Science.
Keywords: Oxovanadium(IV) complexes;DNA binding;DNA photocleavage;Crystal structure;Dithiocarbazate;Phenanthroline bases.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 17 Jul 2008
Last Modified: 19 Sep 2010 04:47
URI: http://eprints.iisc.ernet.in/id/eprint/15073

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