At first glance, interactions between oppositely-charged repeat units on polymers (polyelectrolytes) appear to be well set up for electrostatic attraction. However, it has been known for several decades that polyelectrolyte complexation is largely athermal. The driving force for assembly must therefore be entropic as opposed to Coulombic attraction (electrostatic). The release of counterions and water molecules is the source of the required entropy increase. With the advent of more sensitive thermal analysis techniques, such as isothermal calorimetry, small heats of association have been observed, which provide renewed support for the role of Coulombic interactions in polyelectrolyte complexation. This talk will describe how entropy can be used to assemble or disassemble polyelectrolytes taking them through various morphologies such as tough complexes to liquid-like coacervates. The source of the small enthalpies of association will be identified

Entropy the assembler (of polyelectrolytes)

253rd National Meeting (2017)

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