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Title: Atomic-level engineering and imaging of polypeptoid crystal lattices

Abstract

Rational design of supramolecular nanomaterials fundamentally depends upon an atomic-level understanding of their structure and how it responds to chemical modifications. Here we studied a series of crystalline diblock copolypeptoids by a combination of sequence-controlled synthesis, cryogenic transmission electron microscopy, and molecular dynamics simulation. This family of amphiphilic polypeptoids formed free-floating 2-dimensional monolayer nanosheets, in which individual polymer chains and their relative orientations could be directly observed. Furthermore, bromine atom side-chain substituents in nanosheets were directly visualized by cryogenic transmission electron microscopy, revealing atomic details in position space inaccessible by conventional scattering techniques. While the polypeptoid backbone conformation was conserved across the set of molecules, the nanosheets exhibited different lattice packing geometries dependent on the aromatic side chain para substitutions. Peptoids are inherently achiral, yet we showed that sequences containing an asymmetric aromatic substitution pattern pack with alternating rows adopting opposite backbone chiralities. These atomic-level insights into peptoid nanosheet crystal structure provide guidance for the future design of bioinspired nanomaterials with more precisely controlled structures and properties.

Authors:
ORCiD logo; ORCiD logo; ORCiD logo; ; ; ORCiD logo; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1571319
Grant/Contract Number:  
AC02-05CH11231
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: 116 Journal Issue: 45; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Xuan, Sunting, Jiang, Xi, Spencer, Ryan K., Li, Nan K., Prendergast, David, Balsara, Nitash P., and Zuckermann, Ronald N. Atomic-level engineering and imaging of polypeptoid crystal lattices. United States: N. p., 2019. Web. doi:10.1073/pnas.1909992116.
Xuan, Sunting, Jiang, Xi, Spencer, Ryan K., Li, Nan K., Prendergast, David, Balsara, Nitash P., & Zuckermann, Ronald N. Atomic-level engineering and imaging of polypeptoid crystal lattices. United States. doi:10.1073/pnas.1909992116.
Xuan, Sunting, Jiang, Xi, Spencer, Ryan K., Li, Nan K., Prendergast, David, Balsara, Nitash P., and Zuckermann, Ronald N. Mon . "Atomic-level engineering and imaging of polypeptoid crystal lattices". United States. doi:10.1073/pnas.1909992116.
@article{osti_1571319,
title = {Atomic-level engineering and imaging of polypeptoid crystal lattices},
author = {Xuan, Sunting and Jiang, Xi and Spencer, Ryan K. and Li, Nan K. and Prendergast, David and Balsara, Nitash P. and Zuckermann, Ronald N.},
abstractNote = {Rational design of supramolecular nanomaterials fundamentally depends upon an atomic-level understanding of their structure and how it responds to chemical modifications. Here we studied a series of crystalline diblock copolypeptoids by a combination of sequence-controlled synthesis, cryogenic transmission electron microscopy, and molecular dynamics simulation. This family of amphiphilic polypeptoids formed free-floating 2-dimensional monolayer nanosheets, in which individual polymer chains and their relative orientations could be directly observed. Furthermore, bromine atom side-chain substituents in nanosheets were directly visualized by cryogenic transmission electron microscopy, revealing atomic details in position space inaccessible by conventional scattering techniques. While the polypeptoid backbone conformation was conserved across the set of molecules, the nanosheets exhibited different lattice packing geometries dependent on the aromatic side chain para substitutions. Peptoids are inherently achiral, yet we showed that sequences containing an asymmetric aromatic substitution pattern pack with alternating rows adopting opposite backbone chiralities. These atomic-level insights into peptoid nanosheet crystal structure provide guidance for the future design of bioinspired nanomaterials with more precisely controlled structures and properties.},
doi = {10.1073/pnas.1909992116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 45,
volume = 116,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1909992116

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Works referenced in this record:

Scalable molecular dynamics with NAMD
journal, January 2005

  • Phillips, James C.; Braun, Rosemary; Wang, Wei
  • Journal of Computational Chemistry, Vol. 26, Issue 16, p. 1781-1802
  • DOI: 10.1002/jcc.20289