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• W2037519903 abstract "The reaction of [(H2O)(NH3)5RuII]2+ with calf thymus and salmon sperm DNA has been studied over a wide fange of transition metal ion concentrations. Kinetic studies revealcd a biphasic reaction with an initial fairly rapid coordination of the metal ion being followed by slower reactions. Binding studies were done under pseudo-equilibrium conditions following completion of the initial rapid reaction. Spectra and HPLC of acid-hydrolyzed samples of [(NH3)5RuII]n-DNA prepared by incubation of [(H2O)(NH3)5RuII]2+ with DNA (where [PDNA] = 1.5 mM and reactant [RuII]/[PDNA] ratios were in the fange 0.1 to 0.3) followed by air oxidation showed the predominant binding site on helical DNA to be in the major groove at the N-7 of guanine. The equilibrium constant for [(H2O)(NH3)5RuII]2+ binding to the G7 site in helical CT DNA is 5.1 x 103. Differential pulse voltammetry exhibited a single peak at 48 mV, which is attributed to the reduction of Rum on the G7 sites. At [Run]/[PDNA] <0.5, Tm values for the DNA decreased linearly with increasing ruthenium concentration and an increase in the intensity of the 565 nm dG→ Ru(III) charge transfer band was noted upon melting. The UV and CD spectra of these samples indicated no extensive destacking or alteration in geometry (B family) compared to unsubstituted DNA. At [Run]/[PDNA]〉 0.5 or when single-stranded DNA was used, increased absorbance at 530 nm and 480 nm suggested additional binding to the exocyclic amine sites of adenine and cytosine residues. HPLC and individual spectrophotometric identification of the products derived from hydrolysis of these spec~es yielded both [(Gua)(NH3)5RuIII] and [(Ade)(NH3)5RuIII]. Earlier studies have established the cytidine and adenosine binding sites of [(NH3)5RuIII] to be at their exocyclic amines (C4 and A6). Coordination to these positions indicates disruption of the double helix since these amines are involved in hydrogen bonding on the interior of B-DNA. Agrose gel electrophoresis of superhelical pBR322 plasmid DNA after exposure to various complexes of [(nh3)5Ruiii] in the presence of a reductant and air generally revealed moderately efficient cleavage of the DNA, presumably due to the generation of hydroxyl radical via Fenton's chemistry. However, similar studies involving [(NH3)5RuIII] directly coordinated to the DNA showed no strand cutting above background. Polyacrylamide gel electrophoresis of a 381 bp, 3′-32P-labeled fragment of pBR322 plasmid DNA containing low levels of bound [(NH3)5 RuIII] further indicated negligible DNA cutting by the coordinated metal ion." @default.
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• W2037519903 date "1986-05-01" @default.
• W2037519903 modified "2023-09-26" @default.
• W2037519903 title "Biochemical effects of binding [(H2O)(NH3)5RuII]2+ to DNA and oxidation to[(NH3)5RuIII]n—DNA." @default.
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• W2037519903 doi "https://doi.org/10.1016/s0020-1693(00)82080-0" @default.
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