In this paper, we report the recent advances on precision synthesis, self-assembly, and functions of amphiphilic random copolymers. PEGMA/RMA amphiphilic random copolymers, prepared by living radical copolymerization, formed self-folding polymers in aqueous or organic media. The folding properties were controlled by selecting co-monomers (RMA: hydrophobic DMA, hydrogen-bonding, fluorous) and tuning primary structure (molecular weight, composition).^1-4 PEGMA/DMA random copolymers further afforded precision “intermolecular” self-assembly into uniform nanoparticles in water, where the size, molecular weight, and aggregation number were predictably controlled.⁵ In binary blend, PEGMA/DMA random copolymers with different DMA composition induced self-sorting in water to give discrete nanocompartments with different DMA composition.⁵ Additionally, self-folding amphiphilic random copolymers in water allowed selective intramolecular patching into single-chain crosslinked star polymers with designer cores.⁶

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