Interaction of Cationic 5,10,15,20-Tetrakis(4-N-methyl pyridyl) Porphyrin with Mono- and Polynucleotides: A Study by Picosecond Fluorescence Spectroscopy

摘要

The interaction of water-soluble cationic 5,10,15,20-tetrakis(4-N-methyl pyridyl) porphyrin (H_(2)TMPyP4) with some mono- and polynucleotides is studied by time-resolved and steady-state fluorescence spectroscopy, as well as by steady-state absorption spectroscopy. The fluorescence decay kinetics are analyzed by reconstructing the decay time distributions, which made it possible to describe in more detail than previously the complexes formed due to the interaction. The main effect of binding of H_(2)TMPyP4 to adenosine 5'-monophosphate and to poly(dA-dT)_(2) is shown to be an increase in the fluorescence lifetime from 4.6 ns in the solution to 8.3 and 12.3 ns, respectively. This effect is explained by a less polar (in comparison with water) environment of porphyrin in complexes, which leads to a decrease in the quenching action of the intramolecular charge transfer state between the porphyrin macrocycle and methyl pyridyl groups. In the case of complex formation with guanine-containing nucleotides (guanosine 5'-monophosphate and poly(dG-dC)_(2)), the effect of decrease in the quenching action of the intramolecular charge transfer state caused by a decrease in the medium polarity is superimposed by a stronger effect of decrease in the fluorescence lifetime of porphyrin as a result of intermolecular electron transfer from guanine to excited porphyrin. A high sensitivity of this intermolecular quenching to the mutual arrangement of the electron donor and the electron acceptor makes it possible to reveal four types of complexes between H_(2)TMPyP4 and guanosine 5'-monophosphate, which differ in the positions of four broad peaks in the porphyrin fluorescence decay time distribution (0.1,0.7,2.4, and 6.1 ns). For the complex with poly(dG-dC)_(2), a narrow peak at 2.8 ns prevails in the fluorescence decay time distribution, with the contributions from two additional narrow peaks at 1.0 and 6.2 ns being small.