Precisely Synthesized Sequence-controlled Amino Acid-derived Vinyl Polymers: New Insights into Thermo-responsive Polymer Design
Precisely Synthesized Sequence-controlled Amino Acid-derived Vinyl Polymers: New Insights into Thermo-responsive Polymer Design
复制标题
精确合成序列控制氨基酸衍生乙烯基聚合物：热响应聚合物设计的新见解
DOI：
10.1002/marc.201900550
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
T. Koga
中科院分区：
文献类型：
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作者：
T. Yamano;N. Higashi;T. Koga
热响应嵌段共聚物在生物医学和纳米技术领域引起了极大的兴趣。这些聚合物通过不同热响应块的复杂组合实现了多功能且复杂的响应性。虽然它们的用途很明显，但此类乙烯基聚合物的基本设计原理尚未完全了解。本文报道了序列控制的氨基酸衍生乙烯基聚合物的精确合成及其在水中独特的热响应。七种不同的嵌段（随机）共聚物，包含两种氨基酸嵌段（聚（N-丙烯酰丙氨酸（A）-或甘氨酸（G）-甲酯）），具有相同的总链长度（聚合度[DP] ≈ 30）和化学组成（A/G ≈ 1），但嵌段序列和长度有系统变化，精度目标为 DP ± 1 准备好了。通过指定一级结构，可以微调脱水状态下的热响应，包括转变温度、热敏感性和微环境。这些发现为结构和功能多样化的热响应乙烯基聚合物的设计提供了新的方向。
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.