Charge Regulation Effects in Weak Polyelectrolyte Complexation

August 5, 2025

We are excited to announce the publication of Charge Regulation Effects in Weak Polyelectrolyte Complexation.

We are excited to announce the publication of Charge Regulation Effects in Weak Polyelectrolyte Complexation, published in The Journal of Physical Chemistry Letters. If you are interested, take a look at 

https://doi.org/10.1021/acs.jpclett.5c01877

Abstract:

We use coarse-grained simulations to study the impact of charge regulation on the complexation of a weak polyacid and a strong polycation. Comparing an isolated polyacid with the polyelectrolyte pair, we demonstrate that charge regulation leads to a significant enhancement of the ionization. Furthermore, our simulations unveil that the condensation of isolated chains into a tightly bound complex happens in a discontinuous, first-order like transition as the pH value is varied. These results are corroborated using enhanced sampling calculations, which reveal the presence of a free energy barrier at the transition pH. To quantify the observed charge regulation effects, we compare binding constants of the complex, calculated under charge-regulating and constant charge conditions. We find that charge regulation significantly alters the binding affinity of the complex, emphasizing the importance of including the proper acid–base equilibria in a theoretical description of weak polyelectrolyte complexation.

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