DNA‐Polymer Nanostructures by RAFT Polymerization and Polymerization‐Induced Self‐Assembly

Nanostructures derived from amphiphilic DNA-polymer conjugates have emerged prominently due to their rich self-assembly behavior, however, their synthesis is traditionally challenging. Here, we report a novel platform technology towards DNA-polymer nanostructures of various shapes by leveraging polymerization-induced self-assembly (PISA) for the polymerization from single stranded DNA (ssDNA). A "grafting-from" protocol for thermal reversible addition fragmentation chain transfer (RAFT) polymerization from ssDNA under ambient conditions was developed and utilized for the synthesis of functional DNA-polymer conjugates and DNA-diblock conjugates derived from acrylates and acrylamides. Using this method, PISA was applied for the first time to manufacture isotropic and anisotropic DNA-polymer nanostructrures by varying the chain length of the polymer block. The resulting nanostructures were further functionalized by hybridization with a dye-labelled complementary ssDNA, thus establishing PISA as a powerful route towards intrinsically functional DNA-polymer nanostructures.