Binding, Electrochemical Activation, and Cleavage of DNA by Cobalt(II) Tetrakis-N-methylpyridyl Porphyrin and Its mg src="http://pubs.acs.org/images/gifchars/beta2.gif" border="0" align="midd
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The binding of nucleic acids by water-soluble cobalt(II) tetrakis-N-methylpyridyl porphyrin, (TMPyP)Co, and itshighly electron-deficient derivative cobalt(II) tetrakis-N-methyl pyridyl-mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-octabromoporphyrin, (Br8TMPyP)Co,was investigated by UV-visible absorption, circular dichroism (CD), and electrochemical and gel electrophoresismethods. The changes of the absorption spectra during the titration of these complexes with polynucleotidesrevealed a shift in the absorption maxima and a hypochromicity of the porphyrin Soret bands. The intrinsic bindingconstants were found to be in the range of 105-106 M-1. These values were higher for the more electron-deficient(Br8TMPyP)Co. Induced CD bands were noticed in the Soret region of the complexes due to the interaction ofthese complexes with different polynucleotides, and an analysis of the CD spectra supported a mainly externalmode of binding. Electrochemical studies revealed the cleavage of polynucleotides by (TMPyP)Co and(Br8TMPyP)Co in the presence of oxygen preferentially at the A-T base pair region. Gel electrophoresisexperiments further supported the cleavage of nucleic acids. The results indicate that the mages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-pyrrole brominatedporphyrin, (Br8TMPyP)Co, binds strongly and cleaves nucleic acids efficiently as compared with (TMPyP)Co.This electrolytic procedure offers a unique tool in biotechnology for cleaving double-stranded DNA with specificityat the A-T regions.

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