One-Shot Intrablock Cross-Linking of Linear Diblock Copolymer to Realize Janus-Shaped Single-Chain Nanoparticles.

Developing an efficient and versatile process to transform a single linear polymer chain into a shape-defined nanoobject is a major challenge in the fields of chemistry and nanotechnology to replicate sophisticated biological functions of proteins and nucleic acids in a synthetic polymer system. In this study, we performed one-shot intrablock cross-linking of linear block copolymers (BCPs) to realize single-chain nanoparticles (SCNPs) with two chemically compartmentalized domains (Janus-shaped SCNPs). Detailed structural characterizations of the Janus-shaped SCNP composed of polystyrene-block-poly(glycolic acid) revealed its compactly folded conformation and compartmentalized block localization, similar to the self-folded tertiary structures of natural proteins. Versatility of the one-shot intrablock cross-linking was demonstrated using several different BCP precursors. In addition, the Janus-shaped SCNP produce miniscule microphase-separated structures.