Transformations of Thermosensitive Hyperbranched Poly(ionic liquid)s Monolayers

We synthesized amphiphilic hyperbranched poly­(ionic liquid)­s (HBPILs) with asymmetrical peripheral composition consisting of hydrophobic n-octadecylurethane arms and hydrophilic, ionically linked poly­(N-isopropylacrylamide) (PNIPAM) macrocations and studied low critical solution temperature (LCST)-induced reorganizations at the air–water interface. We observed that the morphology of HBPIL Langmuir monolayers is controlled by the surface pressure with uniform well-defined disk-like domains formed in a liquid phase. These domains are merged and transformed to uniform monolayers with elevated ridge-like network structures representing coalesced interdomain boundaries in a solid phase because the branched architecture and asymmetrical chemical composition stabilize the disk-like morphology under high compression. Above LCST, elevated individual islands are formed because of the aggregation of the collapsed hydrophobized PNIPAM terminal macrocations in a solid phase. The presence of thermoresponsive PNIPAM macrocations initiates monolayer reorganization at LCST with transformation of surface mechanical contrast distribution. The heterogeneity of elastic response and adhesion distributions for HBPIL monolayers in the wet state changed from highly contrasted two-phase distribution below LCST to near-uniform mechanical response above LCST because of the hydrophilic to hydrophobic transformation of the PNIPAM phase.