Competitive interactions of Co(NH3)6(3+) and Na+ with helical B-DNA probed by 59Co and 23Na NMR

59Co NMR is demonstrated to provide a useful probe of the interactions of Co(NH3)6(3+) with helical B-DNA. The association of Co(NH3)6(3+) with B-DNA produces relatively modest effects on the relaxation rate and chemical shift of 59Co, which indicate that the octahedral coordination shell remains intact and that no significant number of long-lived "outer-sphere" complexes are formed at specific sites on the DNA surface. Under conditions where essentially all of the cobalt complex is associated with DNA, the chemical shift of 59Co appears to depend on its binding density. This effect could be due to magnetic heterogeneity in the environments of Co(NH3)6(3+) adjacent to DNA. The local exchange reaction between Co(NH3)6(3+) and Na+ in the vicinity of DNA has been investigated by measuring 59Co chemical shifts and 23Na line widths concurrently. The number of sodium ions displaced by the association of one Co(NH3)6(3+) with DNA cannot be uniquely determined, but the data indicate that this number remains constant over at least the initial stage of a titration of NaDNA with NaCl. 59Co chemical shifts have been analyzed to construct binding isotherms for the association of cobalt hexaammine with DNA over a range of salt (NaCl) concentrations. The magnitudes of the resulting binding constants and their salt dependence are similar to those previously reported for the association of structurally diverse trivalent ligands, such as spermidine and trilysine, with helical nucleic acids. Therefore, these association equilibria appear to be governed primarily by electrostatic interactions.(ABSTRACT TRUNCATED AT 250 WORDS)