The radical addition of mercaptans (RSH) onto poly[2-(3-butenyl)-2-oxazoline], which is available through a living/controlled cationic isomerization polymerization, can proceed smoothly in the absence of side reactions, exhibiting the characteristics of a click reaction. The "thio-click" reaction can be performed under feasible ([RSH]/[CdC] ∼ 1.2-1.5, no transition metal additives) and mild conditions (generation of radicals with UV light at room temperature) and goes to completion within a day. Hydrophobic fluoropolymers can be prepared in the same way as water-soluble (co-)polymers or glycopolymers, starting from readily available materials.

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.

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