The so-called critical condition for polyelectrolyte-colloid complex formation

Complexes formed between oppositely charged polyelectrolytes (PE’s) and either biological or abiotic colloid particles play a central role in such remarkably diverse areas as enzyme immobilization, protein purification, growth factor delivery, personal care products, food formulations and as precursors to coacervates and multilayers. Unlike PE adsorption on oppositely charged planar surfaces—also driven by electrostatics—PE-colloid complexes are often equilibrium states exhibiting reversible formation at a well-defined “critical” colloid surface charge density. We consider how the experimentally observed breadth of this transition, for three polyelectrolyte-colloid systems, is broadened—compared to theoretical expectations—due to (1) colloid (protein) charge anisotropy, (2) colloid (micelle) polydispersity, and (3) colloid (micelle) instability.