Complex Single-chain Polymer Topologies locked by Positionable Twin Disulfide Cyclic Bridges

Olga Shishkan, Mirela Zamfir, Marc A. Gauthier, Hans G. Börner, Jean-François Lutz

In summary, twin disulfide 22-membered rings were studied as positionable bridges for the guided folding of atactic polystyrene chains. Complex bio-hybrid bi-cyclic topologies were obtained by reacting intramolecularly linear precursors containing positionable CRC motifs. Efficient and reagent free folding was observed in all studied cases. In particular, in the studied conditions, intramolecular cyclization was found to be favored as compared to intermolecular reactions. These results confirm that CXC oligomers are highly specific self-associating motifs and emphasize the relevance of these tripeptides for advanced macromolecular engineering. This study also paves the way for designing future water soluble multi-cyclic bio-hybrids,e.g. for enhancing the therapeutic potential of peptide drugs.