Transitions from simple electrolyte to polyelectrolyte in a series of polyphosphates

The dependence of polyelectrolyte characteristics on the number of phosphate groups in a series of polyphosphates was clarified by potentiometric titration and Na-23 nuclear magnetic resonance using the Donnan model. Ca2+ ion binding to various polyphosphates was consistently inhibited as supporting electrolyte concentration increased. The electrostatic interactions between polyions and counterions, which is peculiar to polyelectrolytes, was enhanced by an increase in the number of phosphate groups. The polyelectrolyte characteristics increased non-monotonically with the number of phosphate groups that constituted the molecules, that is, (1) gradual emergence with three or four phosphate groups, (2) marked strengthening from four to eight phosphate groups, and (3) saturation with eight or more phosphate groups. The characteristics of polyelectrolyte molecules comprising eight or more phosphate groups were independent of the degree of polymerization. These interesting behaviors were observed to be closely similar using two quite different experimental techniques, electrochemical titration and nuclear magnetic resonance. (C) 2015 Elsevier B.V. All rights reserved.