Molecularly Designed Interfacial Viscoelasticity by Dendronized Polymers: From Flexible Macromolecules to Colloidal Objects.

The thermodynamic and rheological properties of densely packed dendronized polymers (DPs) at water-air interfaces were studied here for first- and fourth-generation DPs (PG1, PG4) with both small (Pn ≈ 50) and large (Pn ≈ 500) backbone degrees of polymerization. The excellent control over the structural characteristics of these polymers enabled us to investigate how the interfacial properties change as we go from thin, flexible macromolecules toward thicker molecular objects that display colloidal features. The effects of the dendron generation, affecting the persistence length, as well as the degree of polymerization and surface pressure on the formation of DP layers at the water-air interface were studied. Surface pressure measurements and interfacial rheology suggest the existence of significant attractive interactions between the molecules of the higher generation DPs. While all DPs featured reproducible Π-A diagrams, successive compression-expansion cycles and surface pressure relaxation experiments revealed differences in the stability of the formed films, which are consistent with the variations in shape persistence and interactions between the studied DPs. Atomic force microscopy after Langmuir-Blodgett transfer of the films displayed a nanostructuring that can be attributed to the increase in attractive forces with increasing polymer generation and anisotropy. The importance of such structures on the surface properties was probed by interfacial shear rheology, which validated the existence of strong albeit brittle structures for fourth-generation DPs. Ultimately, we demonstrate how in particular rod-like DPs can be used as robust foam stabilizers.