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螺旋聚(苯乙炔)嵌段共聚物的变构模拟自组装及手性传递

Allostery-Mimicking Self-assembly of Helical Poly(phenylacetylene) Block Copolymers and the Chirality Transfer.

机构信息

Beijing National Laboratory for Molecular Science, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.

出版信息

Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9686-9692. doi: 10.1002/anie.202100551. Epub 2021 Mar 18.

Abstract

Allostery can regulate protein self-assembly which further affects biological activities, and achieving precise control over the chiral suprastructures during self-assembly remains challenging. Herein, to mimic the allosterical nature of proteins, the poly(phenylacetylene) block copolymers PPA-b-PsmNap with the dynamic helical backbone were synthesized to investigate their conformational-transition-induced self-assembly. As the helical conformation of the block PsmNap spontaneously transforms from cis-transiod to cis-cisoid, the decreasing solubility of PsmNap blocks in THF induced self-assembly of PPA-b-PsmNap. The self-assembly structures of copolymers can sequentially evolve from vesicles to nanobelts to helical strands during the process of conformation transformation. The screw sense of final helical strands was strictly correlated to the helicity of the block PsmNap. This is helpful to understand the mechanism of allostery-modulated self-assembly.

摘要

变构作用可以调节蛋白质自组装,从而进一步影响生物活性,而在自组装过程中实现对手性超结构的精确控制仍然具有挑战性。在此,为了模拟蛋白质的变构性质,合成了具有动态螺旋主链的聚(苯乙炔)嵌段共聚物 PPA-b-PsmNap,以研究其构象转变诱导的自组装。随着嵌段 PsmNap 的顺反异构自发转变为顺式顺式,PPA-b-PsmNap 中 PsmNap 嵌段在 THF 中的溶解度降低,引发自组装。在构象转变过程中,共聚物的自组装结构可以依次从囊泡演变为纳米带再到螺旋链。最终螺旋链的螺旋方向与嵌段 PsmNap 的螺旋性严格相关。这有助于理解变构调节自组装的机制。

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