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Issue 7, 2003
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Experimental and theoretical study on DNA-binding and photocleavage properties of chiral complexes Δ- and Λ-[Ru(bpy)2L](L =o-hpip, m-hpip and p-hpip)

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Abstract

In order to systematically perform an experimental and theoretical study on DNA-binding and photocleavage properties of chiral complexes Δ- and Λ-[Ru(bpy)2L] (L = o-hpip, m-hpip and p-hpip) on the basis of reported Δ- and Λ-[Ru(bpy)2(o-hpip)] (Δ-1 and Λ-1), a series of novel enantiomerically pure polypyridyl ruthenium(II) complexes, Δ- and Λ-[Ru(bpy)2(m-hpip)](PF6)2 (Δ-2 and Λ-2; bpy = 2,2′-bipyridine, m-hpip = 2-(3-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline), and Δ- and Λ-[Ru(bpy)2(p-hpip)](PF6)2 (Δ-3 and Λ-3, p-hpip = 2-(4-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline), have been synthesized and characterized by elemental analysis, 1H NMR, ESI-MS and CD spectra. The DNA-binding properties of these complexes have been investigated with UV-Vis, emission spectra, CD spectra and viscosity measurements. It is experimentally found that (1) both complexes [Ru(bpy)2(m-hpip)]2+2 and [Ru(bpy)2(p-hpip)]2+3 can bind to DNA with intercalation; (2) for complexes 2 and 3, a subtle but detectable difference was observed in the interaction of these isomers with CT-DNA. The DNA-binding of the Δ-isomer is stronger than that of Λ-isomer, whereas that of Λ-isomer is swifter. (3) Under irradiation with UV light, Ru(II) complexes 2 and 3 can promote almost complete conversion of pBR322 DNA from form I to form II at concentrations of 0.5, 1.0, 0.5, 1.0 (× 10−4M) for Δ-2, Λ-2, Δ-3 and Λ-3, respectively. On the other hand, theoretical calculations for these three isomer complexes have been carried out applying the density functional theory (DFT) method on the level of the B3LYP/LanL2DZ basis set. Some frontier molecular orbital energies and stereographs, as well as a schematic diagram of the energies and related 1MLCT transitions of [Ru(bpy)2L]2+ are presented, and applied to reasonably explain the obtained experimental regularities or trends in the DNA-binding strength or binding constants (Kb) and some spectral properties of the complexes.

Graphical abstract: Experimental and theoretical study on DNA-binding and photocleavage properties of chiral complexes Δ- and Λ-[Ru(bpy)2L] (L = o-hpip, m-hpip and p-hpip)

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Publication details

The article was received on 18 Dec 2002, accepted on 14 Feb 2003 and first published on 03 Mar 2003


Article type: Paper
DOI: 10.1039/B212443B
Citation: Dalton Trans., 2003,0, 1352-1359
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    Experimental and theoretical study on DNA-binding and photocleavage properties of chiral complexes Δ- and Λ-[Ru(bpy)2L] (L = o-hpip, m-hpip and p-hpip)

    W. J. Mei, J. Liu, K. C. Zheng, L. J. Lin, H. Chao, A. X. Li, F. C. Yun and L. N. Ji, Dalton Trans., 2003, 0, 1352
    DOI: 10.1039/B212443B

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