100th Anniversary of Macromolecular Science Viewpoint: Attractive Soft Matter: Association Kinetics, Dynamics, and Pathway Complexity in Electrostatically Coassembled Micelles.

Electrostatically coassembled micelles constitute a versatile class of functional soft materials with broad application potential as, for example, encapsulation agents for nanomedicine and nanoreactors for gels and inorganic particles. The nanostructures that form upon the mixing of selected oppositely charged (block co)polymers and other ionic species greatly depend on the chemical structure and physicochemical properties of the micellar building blocks, such as charge density, block length (ratio), and hydrophobicity. Nearly three decades of research since the introduction of this new class of polymer micelles shed significant light on the structure and properties of the steady-state association colloids. Dynamics and out-of-equilibrium processes, such as (dis)assembly pathways, exchange kinetics of the micellar constituents, and reaction-assembly networks, have steadily gained more attention. We foresee that the broadened scope will contribute toward the design and preparation of otherwise unattainable structures with emergent functionalities and properties. This Viewpoint focuses on current efforts to study such dynamic and out-of-equilibrium processes with greater spatiotemporal detail. We highlight different approaches and discuss how they reveal and rationalize similarities and differences in the behavior of mixed micelles prepared under various conditions and from different polymeric building blocks.