Speaker：Prof.Zhen-Gang Wang

Time：June 12th, 2025 at 13:30 PM

Location: Lecture Room 324,AISMST

Abstract:

Mixing two solutions of oppositely charged polyelectrolytes under appropriate conditions results in a liquid–liquid phase separation into a polymer-rich coacervate phase and a coexisting polymer-poor supernatant phase. This polyelectrolyte complex coacervation (PCC) has received considerable attention in recent years due to its relevance to membraneless organelles in biology, and applications in biomedical and biomimetic systems. The complexation of oppositely charged polymers has been widely believed to be driven by the entropy gain due to counterion release. In this talk, we show that a large portion of the entropy change is due to solvent (water) reorganization, which we can extract by exploiting the temperature dependence of the dielectric constant.  For weakly-to-moderately charged systems under common conditions (monovalent ions, room temperature in aqueous solvent), the solvent reorganization entropy, rather than the counterion release entropy, is the primary entropy contribution. We use this framework to examine the two elementary stages in the symmetric PCC—the complexation between a polycation and polyanion, and the subsequent condensation of the polycation–polyanion pairs by computing the potential of mean-force (PMF) using molecular dynamics simulation. From the calculated PMF, we find that the supernatant phase consists predominantly of polyion pairs with vanishingly small concentration of bare polyelectrolytes, and we provide an estimate of the spinodal of the supernatant phase. Finally, we show that prior to contact, two neutral polyion pairs weakly attract each other by mutually induced polarization, providing the initial driving force for the fusion of the pairs.