• coordination polymers;
  • Hofmeister effect;
  • polyampholytes;
  • polyelectrolytes;
  • polymers;
  • solid polymeric electrolytes


Purely ionic interactions in natural and synthetic macromolecules involve the mutual interaction of fixed charges and their interaction with mobile ions. Such charge-dependent interactions lead to well-documented effects, including chain expansion of polyelectrolytes, globularization of polyampholytes, distributions of mobile ions according to charge screening, or ion condensation models. A variety of structural features, functions, and applications of these systems is amplified by the superimposition of charge-independent effects associated with the occurrence of less polar or hydrophobic groups, special salts, surfactants, or complementary protein assemblies. For instance, ionic and hydrophobic attractive interactions stabilize pearls (or rings)-on-a-string conformations, possibly a model for the formation of the chromatin assembly. The attractive interactions due to hydrophobic fatty acid groups attached to polysaccharides promote the formation of vesicles that entrap and slowly release water-soluble drugs. Intra- and intermolecular associations based on ion-pairing mixed interactions also control the formation of host–guest compounds, protein conformation, and the assembly of layered polyelectrolytes. Metallo-supramolecular polymers and networks are formed due to the coordination of multivalent cations with bi- and trifunctional organic ligands. The association of lithium salts to polymers in the absence of water allows the formation of highly efficient energy sources. It also allows the identification of the ionic species that control charge-independent contributions to Hofmeister effects. This critical review presents a synthetic classification of systems displaying ionic mixed interactions, and a discussion of underlying molecular mechanisms.