Abstract
Abstract The reaction of [H 2 O(NH 3 ) 5 Ru] 2+ with a mixture of tyrosine and valine tRNAs is first order in [P RNA ] and [H 2 O(NH 3 ) 5 Ru] 2+ with k =6.0±0.9 M −1 s −1 . A strong dependence on ionic strength shows ion-pairing to occur during the course of binding. The equilibrium association constant for the binding of [H 2 O(NH 3 ) 5 Ru] 2+ to guanine sites on RNA is K eq =2.9×10 3 . Air oxidation results in the coordination of [(NH 3 ) 5 Ru] 3+ . Signature ligand-to- metal charge transfer bands in the spectra of [(NH 3 ) 5 Ru III ] n -RNA samples provide evidence for binding to A, G and C residues with their relative intensities varying with [Ru]/[P RNA ] in the reaction mixture. Square-wave and cyclic voltammetry revealed two peaks, which are attributed to the Ru III,II couples of RuG, and the sum of RuA and RuC. Consistent with the spectroscopic results, the relative peak currents indicate that [RuG] RNA >;{[RuA] RNA +[RuC] RNA }. The appearance of a new current peak following reduction of [(NH 3 ) 5 Ru III ] n -RNA suggests migration of the metal to endocyclic A sites.
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