Abstract
Single-chain nanoparticles represent an emerging class of nanomaterials designed to mimic protein's folding paradigm. Intrachain covalent crosslinking toward the formation of single-chain nanoparticles encounters complex energy landscapes, leading to the potential occurrence of misfolding issues. While non-covalent crosslinking can circumvent this issue, the resulting single-chain nanoparticles exhibit lower structural stability compared to their covalently crosslinked counterparts. In this study, we present a novel approach for the synthesis of single-chain nanoparticles, achieved through the combination of non-covalent and covalent intramolecular crosslinking. Cyanostilbenes grafted onto the linear polymer form intrachain non-covalent stacks aided by hydrogen bonds, leading to the formation of non-covalently crosslinked single-chain nanoparticles. These nanoparticles undergo conversion to covalently crosslinked nanostructures through subsequent photo-irradiation using [2 + 2] photocycloaddition, a process facilitated by the supramolecular confinement effect. Consequently, the resulting single-chain nanoparticles demonstrate both intrachain folding efficiency and substantial stability, offering significant potential for advancing applications across diverse fields.
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