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Effects of representative group II and transition metal ions on the stability of the poly(dA)·[poly(dT)] 2 triplex were investigated by the van't Hoffplot constructed from a thermal melting curve. The transition, poly(dA)·[poly(dT)] 2 → poly(dA)·poly(dT) + poly(dT), was non-spontaneous with a positive Gibb's free energy, endothermic (ΔH°> 0), and had a favorable entropy change (ΔS° > 0), as seen from the negative slope and positive y-intercept in the van't Hoffplot. Therefore, the transition is driven by entropy change. The Mg 2+ ion was the most effective at stabilization of the triplex, with the effect decreasing in the order of Mg 2+ > Ca 2+ > Sr 2+ >Ba 2+ . A similar stabilization effect was found for the duplex to single strand transition: poly(dA)·poly(dT) + poly(dT) → poly(dA) + 2poly(dT), with a larger positive free energy. The transition metal ions, namely Ni 2+ , Cu 2+ , and Zn 2+ , did not exhibit any effect on triplex stabilization, while showing little effect on duplex stabilization. The different effects on triplex stabilization between group II metal ions and the transition metal ions may be attributed to their difference in binding to DNA; transition metals are known to coordinate with DNA components, including phosphate groups, while group II metal ions conceivably bind DNA via electrostatic interactions. The Cd 2+ ion was an exception, effectively stabilizing the triplex and melting temperature of the third strand dissociation was higher than that observed in the presence of Mg 2+ , even though it is in the same group with Zn 2+ . The detailed behavior of the Cd 2+ ion is currently under investigation.

A Thermodynamic Investigation into the Stabilization of Poly(dA).[poly(dT)]2Triple Helical DNA by Various Divalent Metal Ions

A Thermodynamic Investigation into the Stabilization of Poly(dA).[poly(dT)]₂Triple Helical DNA by Various Divalent Metal Ions