Toward Long-Term-Dispersible, Metal-Free Single-Chain Nanoparticles

We report herein on a new platform for synthesizing stable, inert, and dispersible metal-free single-chain nanoparticles (SCNPs) via intramolecular metal-traceless azide–alkyne click chemistry. It is well known that SCNPs synthesized via Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) often experience metal-induced aggregation issues during storage. Moreover, the presence of metal traces limits its use in a number of potential applications. To address these problems, we selected a bifunctional cross-linker molecule, sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DIBOD). DIBOD has two highly strained alkyne bonds that allow for the synthesis of metal-free SCNPs. We demonstrate the utility of this new approach by synthesizing metal-free polystyrene (PS)-SCNPs without significant aggregation issues during storage, as demonstrated by small-angle X-ray scattering (SAXS) experiments. Notably, this method paves the way for the synthesis of long-term-dispersible, metal-free SCNPs from potentially any polymer precursor decorated with azide functional groups. We gratefully acknowledge Grant PID2021-123438NB-I00 funded by MCIN/AEI/10.13039/501100011033; “ERDF A way of making Europe”, Grant TED2021-130107A-I00 funded by MCIN/AEI/10.13039/501100011033; Unión Europea “NextGenerationEU/PRTR” and Grant IT-1566-22 from Eusko Jaurlaritza (Basque Government).