Micelles of polysoaps: The role of bridging interactions

Polysoaps, hydrophilic polymers incorporating amphiphilic monomers, form intrachain micelles in aqueous media. The micelles are similar to those formed by monomeric amphiphiles but are also endowed with a swollen, starlike corona formed by the spacer chains joining the amphiphiles. Long polysoaps form strings comprising many intrachain micelles. Exchange of amphiphiles between such micelles may give rise to bridging attraction, resulting in the adoption of a collapsed configuration in which the swollen micelles are close packed into a spherical globule. Upon addition of free amphiphiles, this structure unravels in a highly nonlinear fashion. Titration by surfactants, and the resulting swelling, provide information about the configurations of the dilute polysoaps.