pH-Induced Softening of Polyelectrolyte Microcapsules without Apparent Swelling.

Polyelectrolyte microcapsules represent a versatile platform to encapsulate and release active ingredients. Understanding the effect of environmental conditions on the mechanical properties of microcapsules is critically important for enabling their applications under various settings. In this report, we investigate the effect of solution pH on the mechanical properties of polyelectrolyte microcapsules made of two weak polyelectrolytes (poly(acrylic acid) and branched poly(ethylenimine)), formed via recently introduced nanoscale interfacial complexation in emulsion (NICE). Interestingly, the stiffness of the NICE microcapsule shell is reduced significantly (by 2 orders of magnitude) when the solution pH is raised from 2 to 6 even though there is little change in the size of microcapsules. These seemingly counterintuitive results suggest that the molecular structure of NICE microcapsules may be different from those of conventional polyelectrolyte microcapsules. The possibility of tuning the shell stiffness without inducing significant changes in the microcapsule size could offer unique advantages in practical applications.