Ultrafast, Robust, and Reversible Self-Assembled Nanofibers via Thiolactone Chemistry Strategy

Small. 2025 Jan 7:e2411982. doi: 10.1002/smll.202411982. Online ahead of print.

Abstract

Self-assembly in supramolecular chemistry is crucial for nanostructure creation but faces challenges like slow speeds and lack of reversibility. In this study, a novel comb-like polymer poly(amide sulfide) (PAS) based on thiolactone chemistry is reported, which rapidly self-assemble into stable nanofibers, offering excellent robustness and reversibility in the self-assembled structure. The PAS backbone contains pairs of amide bonds, each linked to an alkyl side chain in a controlled 2:1 ratio. The polymer rapidly forms fibrillar micelles driven by the hydrophobic side chains and then undergoes hydrogen-bonded cross-linking between the main-chain amide bonds to form stable nanofibers. N, N-dimethylacetamide/LiCl solution allows for reversible regulation of nanofiber self-assembly, without altering the fiber properties. It is anticipated that this line of research will enrich the field of macromolecular self-assembly with important advances toward the realization of ultrafast, robust, and reversible self-assembly systems.

Keywords: hydrogen bonds; hydrophobic interactions; nanofibers; thiolactone; ultrafast self‐assembly.