Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs
Abstract
Hierarchical nanomaterials have received increasing interest for many applications. Here, we report a facile programmable strategy based on an embedded segmental crystallinity design to prepare unprecedented supramolecular planar nanobrush-like structures composed of two distinct molecular packing motifs, by the self-assembly of one particular diblock copolymer poly(ethylene glycol)-block-poly(N-octylglycine) in a one-pot preparation. We demonstrate that the superstructures result from the temperature-controlled hierarchical self-assembly of preformed spherical micelles by optimizing the crystallization-solvophobicity balance. Particularly remarkable is that these micelles first assemble into linear arrays at elevated temperatures, which, upon cooling, subsequently template further lateral, crystallization-driven assembly in a living manner. Addition of the diblock copolymer chains to the growing nanostructure occurs via a loosely organized micellar intermediate state, which undergoes an unfolding transition to the final crystalline state in the nanobrush. This assembly mechanism is distinct from previous crystallization-driven approaches which occur via unimer addition, and is more akin to protein crystallization. Interestingly, nanobrush formation is conserved over a variety of preparation pathways. The precise control ability over the superstructure, combined with the excellent biocompatibility of polypeptoids, offers great potential for nanomaterials inaccessible previously for a broad range of advanced applications.
- Authors:
-
[1];
[1];
[2];
[1];
[1];
[3];
[4]
- Key Laboratory of Biobased Polymer Materials, College of Polymer Science and Engineering, Qingdao University of Science and Technology, 266042 Qingdao, China,
- Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720,
- Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 130022 Changchun, China,
- Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Natural Science Foundation of Shandong Province
- OSTI Identifier:
- 1848023
- Alternate Identifier(s):
- OSTI ID: 1985023
- Grant/Contract Number:
- AC02-05CH11231; 51722302; 21674054; ZR2019JQ17
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 117 Journal Issue: 50; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; self-assembly; polypeptoid; diblock copolymer; crystallization; solvophobicity
Citation Formats
Sun, Jing, Wang, Zhiwei, Zhu, Chenhui, Wang, Meiyao, Shi, Zhekun, Wei, Yuhan, Fu, Xiaohui, Chen, Xuesi, and Zuckermann, Ronald N. Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs. United States: N. p., 2020.
Web. doi:10.1073/pnas.2011816117.
Sun, Jing, Wang, Zhiwei, Zhu, Chenhui, Wang, Meiyao, Shi, Zhekun, Wei, Yuhan, Fu, Xiaohui, Chen, Xuesi, & Zuckermann, Ronald N. Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs. United States. https://doi.org/10.1073/pnas.2011816117
Sun, Jing, Wang, Zhiwei, Zhu, Chenhui, Wang, Meiyao, Shi, Zhekun, Wei, Yuhan, Fu, Xiaohui, Chen, Xuesi, and Zuckermann, Ronald N. Tue .
"Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs". United States. https://doi.org/10.1073/pnas.2011816117.
@article{osti_1848023,
title = {Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs},
author = {Sun, Jing and Wang, Zhiwei and Zhu, Chenhui and Wang, Meiyao and Shi, Zhekun and Wei, Yuhan and Fu, Xiaohui and Chen, Xuesi and Zuckermann, Ronald N.},
abstractNote = {Hierarchical nanomaterials have received increasing interest for many applications. Here, we report a facile programmable strategy based on an embedded segmental crystallinity design to prepare unprecedented supramolecular planar nanobrush-like structures composed of two distinct molecular packing motifs, by the self-assembly of one particular diblock copolymer poly(ethylene glycol)-block-poly(N-octylglycine) in a one-pot preparation. We demonstrate that the superstructures result from the temperature-controlled hierarchical self-assembly of preformed spherical micelles by optimizing the crystallization-solvophobicity balance. Particularly remarkable is that these micelles first assemble into linear arrays at elevated temperatures, which, upon cooling, subsequently template further lateral, crystallization-driven assembly in a living manner. Addition of the diblock copolymer chains to the growing nanostructure occurs via a loosely organized micellar intermediate state, which undergoes an unfolding transition to the final crystalline state in the nanobrush. This assembly mechanism is distinct from previous crystallization-driven approaches which occur via unimer addition, and is more akin to protein crystallization. Interestingly, nanobrush formation is conserved over a variety of preparation pathways. The precise control ability over the superstructure, combined with the excellent biocompatibility of polypeptoids, offers great potential for nanomaterials inaccessible previously for a broad range of advanced applications.},
doi = {10.1073/pnas.2011816117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 50,
volume = 117,
place = {United States},
year = {Tue Dec 15 00:00:00 EST 2020},
month = {Tue Dec 15 00:00:00 EST 2020}
}
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