Sequestration of Small Ions and Weak Acids and Bases by a Polyelectrolyte Complex Studied by Simulation and...

Mixing of oppositely charged polyelectrolytes can result in phase separation into a polymer-poor supernatant and a polymer-rich polyelectrolyte complex (PEC). We present a new coarse-grained model for the Grand-reaction method that enables us to determine the composition of the coexisting phases in a broad range of pH and salt concentrations. We validate the model by comparing it to recent simulations and experimental studies, as well as our own experiments on poly(acrylic acid)/poly(allylamine hydrochloride) complexes. The simulations using our model predict that monovalent ions partition approximately equally between both phases, whereas divalent ones accumulate in the PEC phase. On a semiquantitative level, these results agree with our own experiments, as well as with other experiments and simulations in the literature. In the sequel, we use the model to study the partitioning of a weak diprotic acid at various pH values of the supernatant. Our results show that the ionization of the acid is enhanced in the PEC phase, resulting in its preferential accumulation in this phase, which monotonically increases with the pH. Currently, this effect is still waiting to be confirmed experimentally. We explore how the model parameters (particle size, charge density, permittivity, and solvent quality) affect the measured partition coefficients, showing that fine-tuning of these parameters can make the agreement with the experiments almost quantitative. Nevertheless, our results show that charge regulation in multivalent solutes can potentially be exploited in engineering the partitioning of charged molecules in PEC-based systems at various pH values.