Poly(2-alkyl-2-oxazoline)s can be regarded as pseudo-peptides or bioinspired polymers, which are available through living/controlled cationic polymerization and polymer ("click") modification procedures. Materials and solution properties may be adjusted via the nature of the side chain (hydrophilic-hydrophobic, chiral, bio-functional, etc.), opening the way to stimulus-responsive materials and complex colloidal structures in aqueous environments. Herein, we give an overview over the macromolecular engineering of polyoxazolines, including the synthesis of biohybrids, and the "smart"/bioinspired aggregation behavior in solution.
Great balls of fiber! Annealing of a dilute aqueous solution of poly(2‐isopropyl‐2‐oxazoline) above its cloud point leads to the formation of a coagulate in the form of crystalline nanofibers (see microscopy image). Directional crystallization, which occurs below the glass transition temperature of the polymer at 65 °C, is driven by hydrophobic and dipolar interactions in combination with a solvation effect.
Annealing of dilute aqueous solutions of poly(2-isopropyl-2oxazoline) at above the cloud point leads to the irreversible formation of coagulate particles with hierarchical ordering on two length-scales: micron-sized assemblies of fibrils that measure tens of nanometres across.
Using fluorescence super-resolution microscopy we studied simultaneous spectral, spatial localization, and blinking behavior of individual 1D J-aggregates. Excitons migrating 100 nm are funneled to a trap appearing as an additional red-shifted blinking fluorescence band. We propose that the trap is a Frenkel exciton state formed much below the main exciton band edge due to an environmentally induced heavy-tailed Lévy disorder. This points to disorder engineering as a new avenue in controlling light-harvesting in molecular ensembles.
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