Reactivity Control of Polymer Functional Groups by Altering the Structure of Thermoresponsive Triblock Copolymers

Reactivity Control of Polymer Functional Groups by Altering the Structure of Thermoresponsive Triblock Copolymers
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DOI:
10.1021/acsomega.9b01816
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发表时间:
2019-10-08
期刊:
影响因子:
4.1
通讯作者:
Ito, Yoshihiro
Ito, Yoshihiro
中科院分区:
化学3区
文献类型:
--
作者:
Akimoto, Jun;Tamate, Ryota;Ito, Yoshihiro

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合成了一种热响应性ABA三嵌段共聚物,在热响应性A链段上含醛基团。在较低的临界溶液温度(LCST)以上,由于热响应链段的疏水相互作用,聚合物形成了胶束组装。相反,当温度降低到LCST以下时,ABA聚合物组装件就会分解。利用这种结构变化,研究了醛基团与伯胺白蛋白和聚烯丙胺的反应性。当ABA聚合物组装体和反应物混合在LCST上方时,由于醛被疏水的热响应核心保护,席夫碱的形成被抑制。相反,在LCST以下,证实了ABA三嵌段共聚物与分子上的伯胺部分之间形成了席夫碱。因此,可以通过改变热响应性ABA聚合物的结构来控制醛官能团的反应性。
A thermoresponsive ABA triblock copolymer bearing an aldehyde group on the thermoresponsive A segments was synthesized. The polymer formed a micellar assembly due to the hydrophobic interactions of the thermoresponsive segment above the lower critical solution temperature (LCST). In contrast, the ABA polymer assembly decomposed upon lowering the temperature below the LCST. Using this structural change, the reactivity of the aldehyde group toward primary amines of albumin and poly(allylamine) was investigated. When the ABA polymer assembly and reactant were mixed above the LCST, Schiff base formation was suppressed because of the aldehyde group being protected by the hydrophobic thermoresponsive core. In contrast, Schiff base formation between the ABA triblock copolymer and the primary amine moiety on the molecules was confirmed below the LCST. The reactivity of the aldehyde functional group can therefore be controlled by altering the structure of the thermoresponsive ABA polymer.