Precisely Synthesized Sequence‐Controlled Amino Acid–Derived Vinyl Polymers: New Insights into Thermo‐Responsive Polymer Design

Abstract Thermo‐responsive block copolymers are of great interest in biomedical and nanotechnological fields. These polymers achieve a versatile and complex responsiveness through a sophisticated and intricate combination of different thermo‐responsive blocks. While their utility is clear, the fundamental design principles of such vinyl polymers are not yet thoroughly understood. Herein, a precise synthesis of sequence‐controlled amino‐acid‐derived vinyl polymers and their unique thermal response in water are reported. Seven distinct block (random) copolymers that contain two kinds of amino acid blocks (poly( N ‐acryloyl alanine( A )‐ or glycine( G )‐methyl ester)) with the same total chain length (degree of polymerization [DP] ≈30) and chemical composition ( A / G ≈1), but with systematic variations in the block sequence and length, with an accuracy target of DP ± 1, are prepared. By specifying the primary structure, the thermal responses including transition temperature, thermo‐sensitivity, and microenvironment in the dehydrated state can be finely tuned. These findings offer new directions in the design of structurally and functionally diverse thermo‐responsive vinyl polymers.