Influence of pH on the formation of a polyelectrolyte complex by dissipative particle dynamics simulation: From an extended to a compact shape.

This work aims to investigate the influence of pH on the mechanism of assembly of macromolecules. We studied the effect of the pH on the interaction of two polyelectrolytes of opposed charge, having the same size, by means of dissipative particle dynamics method. The system consisted of a strong cationic and a weak anionic polyelectrolyte in an aqueous solution containing monovalent counterions. The analysis was made by varying the pH of the solution, which modifies the charge fraction of the weak anionic polyelectrolyte with a dissociation acid constant pKa of 5.5, while the polycation is fully charged in all the pH range used, characteristic of a strong polyelectrolyte. In order to describe the influence of pH on the complexation process, we have analyzed the pair radial distribution functions polyanion-counterion, polycation-counterion, and polyanion-polycation. The complex conformation was studied by means of the radius of gyration and the end-to-end distance of both chains as the pH varied from 1 to 14. A relevant finding obtained here was the relationship between the radial distribution functions and the counterion release from the polyelectrolytes, which leads to a reduction in the size of the complex when pH increased. Surprisingly, a transition from an extended to a compact polyelectrolyte complex was obtained when the pH reached the dissociation acid constant pKa of the weak polyelectrolyte. This systematic study can help to understand a large number of more realistic problems in biological systems such as protein complex, chromatin phase transition, or in complex systems applied in biomedical science.