4.8 Article

Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 15, 页码 5890-5902

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c01088

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资金

  1. National Science Foundation [CHE 1609447, 2003458]
  2. National Natural Science Foundation of China [52073025]
  3. Northwestern University
  4. Dow Chemical Company
  5. E.I. DuPont de Nemours Co.
  6. DOE Office of Science [DE-AC02-06CH11357]
  7. U.S. DOE, Office of Science, Office of Basic Energy Sciences [DE-SC0012704]
  8. National Institutes of Health, National Institute of General Medical Sciences [P41 GM111244]
  9. DOE Office of Biological and Environmental Research [KP1605010]
  10. NIH [S10 OD012331]
  11. Division Of Chemistry
  12. Direct For Mathematical & Physical Scien [2003458] Funding Source: National Science Foundation

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The study investigates the influence of N-substituent structure on the crystalline packing and hierarchical self-assembly of diblock copolypeptoids. It reveals that the linear versus branched N-substituent architecture significantly impacts the supramolecular self-assembly of diblock copolypeptoids in solution, leading to tunable geometry and hierarchical structure of polypeptoid-based nanomaterials.
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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