Weakly Charged Polyelectrolytes: Collapse Induced by Extra Ionization

Several experimental facts indicate that the collapse transition in weakly charged polyelectrolyte gels or single macromolecules can take place with an increase in the degree of ionization (e.g., during titration of a weak polyacid). This unusual behavior can be explained by the energy gain from the formation of ion pairs in the collapsed state of low polarity, which competes with the swollen state where most of the counterions are dissociated. An increasing degree of ionization increases the thermodynamic advantages of the collapsed state with an ionomeric multiplet structure over the swollen polyelectrolyte state. In some regimes, this effect can lead to reentrant phase transition behavior, i.e., to an initial decollapse of the gel upon charging with subsequent jumplike collapse at a higher fraction of charged monomer units.