Zhen-Gang Wang

Origin of the Entropic Driving Force in Polyelectrolyte Complex Coacervation

Zhen-Gang Wang
Division of Chemistry and Chemical Engineering
California Institute of Technology

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.

Bio: Zhen-Gang Wang received his B.Sc. in Chemistry in 1982 from Beijing (Peking) University, and his Ph.D. in Chemistry in 1987 from the University of Chicago. He did postdoctoral research first in Exxon Research and Engineering Company and then at UCLA. Since 1991 he has been on the Chemical Engineering faculty at the California Institute of Technology, where he is currently the Dick and Barbara Dickinson Professor and Executive Officer of Chemical Engineering.

Wang’s research is the theoretical and computational study of structures, phase behavior, interfacial properties and dynamics of polymers, soft materials, and biophysical systems. His current activities revolve around three main themes: charged systems, including polyelectrolytes, salt-doped polymers, and electric double layers; nucleation or more generally barrier crossing in polymers and soft matter; and nonlinear rheology of polymer gels and entangled polymers.

Wang is a fellow of the American Physical Society, and has received several awards and honors, including the Camille Dreyfus Teacher–Scholar Award (1995), the Alfred P. Sloan Award (1996), the Braskem Award from the American Institute of Chemical Engineers (AIChE) (2018), the AIChE Alpha Chi Sigma Award (2023), and the APS Polymer Physics Prize (2024). In 2008, he was awarded the Richard P. Feynman Prize for Excellence in Teaching, Caltech’s highest teaching honor.