Polarography of polynucleotides. 3. Polyadenylic acid: the electrode process and interaction with polyamines

Polyadenylic acid (poly A) was studied under various conditions using both DC polarography and phase sensitive AC polarography and by measuring the time-course of the current during the lifetime of a single drop of the dropping mercury electrode. Under certain conditions the current at potentials of the limiting portion of the DC polarographic wave does not reach its limiting value and in extreme situations peak-shaped curves are observed. This phenomenon is explained in terms of desorption and repulsion from the electrode of neutral poly A due to its polyanionic character. Consequently, the suppression of the current can be enhanced by increasing negative potential of the electrode and by exposing the negative charges of phosphate groups, e.g., by increasing pH and temperature and by decreasing ionic strength and buffer capacity; vice versa, the current suppression can be at least partially eliminated by reversing these conditions. Polyamines which seem to shield the phosphate groups through specific interactions are very effective in eliminating the current suppression. The effectiveness of a polyamine is determined by its chain length and by the density of its amino groups and the geometry of their distribution.