Journal of Biomolecular Structure and Dynamics 2011-12-01

Effect of the alkaline cations on the stability of the model polynucleotide poly(dG-dC)·poly(dG-dC).

Marta Airoldi, Giuseppe Gennaro, Marcello Giomini, Anna Maria Giuliani, Mauro Giustini

Index: J. Biomol. Struct. Dyn. 29 , 585-594, (2011)

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Abstract

When the model polynucleotide poly(dG-dC)∙poly(dG-dC) [polyGC] is titrated with a strong acid (HCl) in unbuffered aqueous solutions containing the chlorides of the alkali metals in the concentration range 0.010 M-0.600 M, two transitions in the absorbance vs. pH plots are evidenced, characterized by the constants pK(a(₁)) and pK(a(₂)). The limiting values at infinite saline concentrations of these two constants, namely pK(∞)(a(₁)) and pK(∞)(a(₂)) obtained making use of the "one site saturation constant" equation or, in turn, of the double logarithmic plot: pK(a) vs. log([salt]⁻¹), exhibit a clear dependence on the nature of the cations. The effects of the different alkali cations on the pK(∞)(a) values follow the Hofmeister series. In fact, the pK(∞)(a(₁)) and the pK(∞)(a(₂)) values are smaller for Li+ and Na+ than for Rb+ and Cs+, with K+ at the border between the two, showing that the transitions require higher concentrations of protons to occur in the presence of high concentrations of the cosmotropic ions.