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Dalton Transactions Vol - 0 Issue - 5

DNA binding and oxidative DNA cleavage activity of (μ-oxo)diiron(iii) complexes in visible light

Content Provider	Royal Society of Chemistry (RSC)
Author	Chakravarty, Akhil R. Roy, Mithun Santhanagopal, Ramkumar
Copyright Year	2009
Abstract	Four (μ-oxo)diiron(III) complexes [Fe2(μ-O)(H2O)2B4](ClO4)4 (1 and 2) and [Fe2(μ-O)(μ-O2CMe)B4](ClO4)3 (3 and 4), where B = 1,10-phenanthroline (phen) and dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq), are prepared and their DNA binding and cleavage activity studied. The complexes show DNA binding propensity giving Kb values of 3.6–9.3 × 104 M−1. The viscosity and DNA melting data suggest a surface and/or groove binding nature of the complexes to calf thymus (CT) DNA. The DNA binding data obtained from isothermal calorimetric study indicate two binding modes involving surface aggregation and/or partial intercalation of the phenanthroline bases to CT DNA. All the complexes show chemical nuclease activity in the presence of 3-mercaptopropionic acid as a reducing agent following a mechanistic pathway that involves formation of superoxide and hydroxyl radicals. Photoirradiation of pUC19 DNA at 365 nm in the presence of 1–4 show that the complexes, barring 1, are efficient photocleavers of supercoiled DNA to its nicked circular form. Complexes 2–4 display photocleavage activity in visible light of different wavelengths. Complexes 3 and 4 exhibit significant DNA cleavage activity in red light of 633 nm, the wavelength known for the activity of the photodynamic therapeutic drug Photofrin®. The mechanistic study using various additives suggests a minor groove binding nature of the complexes with the formation of singlet oxygen from the quinoxaline moiety of dpq and hydroxyl radical from photodecarboxylation of the acetate ligand as the reactive oxygen species.
Starting Page	1024
Ending Page	1033
Page Count	10
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	0
Issue Number	6
Journal	Dalton Transactions
DOI	10.1039/b815215b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Water Phenanthroline Quinoxaline DNA Viscosity Nucleic acid thermodynamics Thymus Contour line Nuclease Acid Redox Superoxide Hydroxy group PUC19 Wavelength Porfimer sodium Singlet oxygen Hydroxyl radical Ligand Reactive oxygen species
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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