Abstract
Spontaneous phase separation, or coacervation, of oppositely charged macromolecules is a powerful and ubiquitous mechanism for the assembly of natural and synthetic materials. Two critical triggering phenomena in coacervation science and technology are highlighted here. The first is the transition from one (mixed) to two (separated) phases of polyelectrolytes coacervated with small molecules upon the addition of one or two charges per molecule. The second is a large jump in coacervate modulus and viscosity mediated by the addition of just one additional charge to a three-charged system. This previously unknown viscoelastic transition is relevant to those aspects of disease states that are characterized by abnormal mechanical properties and irreversible assembly.