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

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.