Interactions of meso-tetra-(4-N-oxyethylpyridyl) porphyrin (TOEPyP(4)), its 3-N analog (TOEPyP(3)) and their Co, Cu, Ni, Zn metallocomplexes with duplex DNA have been investigated by uv/visible absorbance and circular dichrosim spectroscopies. Results reveal the interactions of these complexes with duplex DNA are of two types. (1) External binding of duplex DNA by metalloporphyrins containing Zn and Co, and (2) Binding of duplex DNA both externally and internally (by intercalation) by porphyrins not containing metals, and metalloporphyrins containing Cu and Ni. Results indicate that (4N-oxyethylpyridyl) porphyrins intercalate more preferably in the structure of duplex DNA and have weaker external binding than 3N-porphyrins.
The influence of water soluble cationic meso-tetra(4N-hydroxyethyl)pyridyl porphyrin ( H 2 THOEtPyP 4) and it's metal complexes with Ni ( II ), Cu ( II ), Co ( II ) and Zn ( II ) on hydrodynamic and spectral behavior of DNA solutions has been studied by viscometry and UV-vis absorption methods. It was shown that the presence of planar porphyrins, such as H 2 THOEtPyP 4, NiTHOEtPyP 4 and CuTHOEtPyP 4 leads to an increase in viscosity at relatively small concentrations, and then decreases to stable values. Such behavior corresponds to intercalation of these porphyrins in DNA structure, which results in a decrease of helical twist and lengthening of the DNA molecule. In the case of porphyrins with axial ligands, such as ZnTHOEtPyP 4 and CoTHOEtPyP 4, the relative viscosity decreases, which is explained by self-stacking of these porphyrins on DNA surface. Calculation and interpretation of binding parameters (Kb and n) demonstrated good agreement of viscometric and spectrophotometric measurements.
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