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The concept for thermal RAFT polymerization from ssDNA under ambient conditions by using enzyme degassing is depicted. BTPA‐functionalized ssDNA served as the CTA in RAFT polymerization for the generation of functional DNA–homo and –diblock copolymer conjugates. Moreover, DNA–polymer nanostructures of various shapes were obtained by leveraging polymerization‐induced self‐assembly from ssDNA, establishing a new platform technology towards functional DNA–polymer nanostructures.
