Thermosensitive polymers show an entropy-driven transition from a well-solvated to a poorly solvated polymer chain, resulting in a more compact globular conformation. The transition at the lower critical solution temperature (LCST) is often sharp, which allows for a wide range of smart material applications. At the LCST, oligo(ethylene glycol)-substituted polyisocyanides (PICs) form soft hydrogels, composed of polymer bundles similar to biological gels, such as actin, fibrin and intermediate filaments. Here, we show that the LCST of PICs strongly depends linearly on the length of the ethylene glycol (EG) tails; every EG group increases the LCST and thus the gelation temperature by nearly 30 °C. Using a copolymerisation approach, we demonstrate that we can precisely tailor the gelation temperature between 10 °C and 60 °C and, consequently, tune the mechanical properties of the PIC gels.@en

Control over the organization of assemblies from molecular dimensions up to the macroscopic length scale is an outstanding challenge in science, above all for materials in high dilution. Instead of inducing order by generating very long and stiff structures, an alternative approach is studied: a two-component assembly of a semiflexible polymer with a (self-assembling) chromonic liquid crystal. By following the structure formation in time using different techniques, a mechanistic model is proposed that explains how such unusually well-defined materials can be created from flexible components. It is concluded that at this very low concentration (>99.6% water), these macroscopically organized structures can only be formed when the energies between different assembly states and their interconversion rates are properly balanced. This may, however, be in reach for a wide range of materials, which makes this a generic route toward high definition at low concentration without the need for long and rigid building blocks.@en