Evidence of Many-Body Interactions in the Virial Coefficients of Polyelectrolyte Gels

Simulation studies of aqueous polymer solutions, and heuristic arguments by De Gennes for aqueous polyethylene oxide polymer solutions, have suggested that many-body interactions can give rise to the 'anomalous' situation in which the second osmotic virial coefficient is positive, while the third virial coefficient is negative. This phenomenon was later confirmed in analytic calculations of the phase behavior and the osmotic pressure of complex fluids exhibiting cooperative self-assembly into extended dynamic polymeric structures by Dudowicz et al. In the present study, we experimentally confirm the occurrence of this osmotic virial sign inversion phenomenon for several highly charged model polyelectrolyte gels (poly(acrylic acid), poly(styrene sulfonate), DNA, hyaluronic acid), where the virial coefficients are deduced from osmotic pressure measurements. Our observations qualitatively accord with experimental and simulation studies indicating that polyelectrolyte materials exhibit supramolecular assembly in solution, another symptomatic property of fluids exhibiting many-body interactions. We also find that the inversion in the variation of the second (A₂) and third (A₂) virial coefficients upon approach to phase separation does not occur in uncharged poly(vinyl acetate) gels. Finally, we briefly discuss the estimation of the osmotic compressibility of swollen polyelectrolyte gels from neutron scattering measurements as an alternative to direct, time-consuming and meticulous osmotic pressure measurements. We conclude by summarizing some general trends and suggesting future research directions of natural and synthetic polyelectrolyte hydrogels.