Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern.
Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern.
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侧链支化模式调控两亲性多肽嵌段共聚物的分子构型和溶液自组装。
DOI：
10.1021/jacs.1c01088
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发表时间：
2021-04-21
影响因子：
15
通讯作者：
Zhang D
中科院分区：
文献类型：
--
作者：
Kang L;Chao A;Zhang M;Yu T;Wang J;Wang Q;Yu H;Jiang N;Zhang D
螺旋状结晶二嵌段共聚类肽的溶液自组装由于其能够形成具有可定制的形貌和功能的分级纳米结构而受到越来越多的关注。虽然已知N-取代基（或侧链）结构会影响类多肽的结晶，但它们在决定二嵌段共聚类多肽的分级溶液自组装中的作用尚未完全理解。在此，我们设计并合成了两种类型的二嵌段共聚肽，即，聚（N-甲基甘氨酸）-b-聚（N-辛基甘氨酸）（PNMG-b-PNOG）和聚（N-甲基甘氨酸）-b-聚（N-2-乙基-1-己基甘氨酸）（PNMG-b-PNEHG），研究N-取代基结构对二嵌段共聚类肽在甲醇中的结晶堆积和分级自组装的影响。随着线性脂肪族N-取代基，PNOG嵌段包装成具有板状分子几何形状的高度有序的晶体结构，导致PNMG-b-PNOG分子自组装成由径向排列的纳米颗粒亚基组成的分级微花形态。相比之下，PNEHG嵌段带有庞大的支链脂肪族N-取代基是棒状的，并且优选堆叠成柱状六方液晶中间相，这驱动PNMG-b-PNEHG分子在溶液中自组装成对称的六方纳米片。时间依赖性小/广角X射线散射和显微成像分析的组合进一步揭示了形成这些微米花和六边形纳米片的自组装机制。这些结果突出了N-取代基结构的显著影响（即，线性与支化）对溶液中二嵌段共聚类肽的超分子自组装的影响，这可以作为一种有效的策略来调整基于类肽的纳米材料的几何形状和分级结构。
Solution self-assembly of coil-crystalline diblock copolypeptoids has attracted increasing attention due to its capability to form hierarchical nanostructures with tailorable morphologies and functionalities. While the N-substituent (or side chain) structures are known to affect the crystallization of polypeptoids, their roles in dictating the hierarchical solution self-assembly of diblock copolypeptoids are not fully understood. Herein, we designed and synthesized two types of diblock copolypeptoids, i.e., poly(N-methylglycine)-b-poly(N-octylglycine) (PNMG-b-PNOG) and poly(N-methylglycine)-b-poly(N-2-ethyl-1-hexylglycine) (PNMG-b-PNEHG), to investigate the influence of N-substituent structure on the crystalline packing and hierarchical self-assembly of diblock copolypeptoids in methanol. With a linear aliphatic N-substituent, the PNOG blocks pack into a highly ordered crystalline structure with a board-like molecular geometry, resulting in the self-assembly of PNMG-b-PNOG molecules into a hierarchical microflower morphology composed of radially arranged nanoribbon subunits. By contrast, the PNEHG blocks bearing bulky branched aliphatic N-substituents are rod-like and prefer to stack into a columnar hexagonal liquid crystalline mesophase, which drives PNMG-b-PNEHG molecules to self-assemble into symmetrical hexagonal nanosheets in solution. A combination of time-dependent small/wide-angle X-ray scattering and microscopic imaging analysis further revealed the self-assembly mechanisms for the formation of these microflowers and hexagonal nanosheets. These results highlight the significant impact of the N-substituent architecture (i.e., linear versus branched) on the supramolecular self-assembly of diblock copolypeptoids in solution, which can serve as an effective strategy to tune the geometry and hierarchical structure of polypeptoid-based nanomaterials.
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