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Title: Evidence for cis Amide Bonds in Peptoid Nanosheets

Abstract

Peptoid nanosheets are supramolecular protein-mimetic materials that form from amphiphilic polypeptoids with aromatic and ionic side chains. Nanosheets have been studied at the nanometer scale, but the molecular structure has been difficult to probe. We introduce the use of 13C-13C dipolar recoupling solid-state NMR measurements to reveal the configuration of backbone amide bonds selected by 13C isotopic labeling of adjacent α-carbons. Measurements on the same molecules in the amorphous state and in nanosheets revealed that amide bonds in the center of the amino block of peptoid (NaeNpe)7-(NceNpe)7(B28) favor the trans configuration in the amorphous state and the cis configuration in the nanosheet. This unexpected conclusion contrasts with previous NMR and theoretical studies of short solvated peptoids. Moreover, examination of the amide bond at the junction of the two charged blocks within B28 revealed a mixture of both cis and trans configurational states, consistent with the previously predicted brickwork-like intermolecular organization.

Authors:
 [1];  [2];  [2];  [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [1]
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  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Defense Threat Reduction Agency (DTRA); Georgia Inst. of Technology
OSTI Identifier:
1515161
Grant/Contract Number:  
AC02-05CH11231; DTRA10027-15875
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 10; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hudson, Benjamin C., Battigelli, Alessia, Connolly, Michael D., Edison, John, Spencer, Ryan K., Whitelam, Stephen, Zuckermann, Ronald N., and Paravastu, Anant K. Evidence for cis Amide Bonds in Peptoid Nanosheets. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b01040.
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Hudson, Benjamin C., Battigelli, Alessia, Connolly, Michael D., Edison, John, Spencer, Ryan K., Whitelam, Stephen, Zuckermann, Ronald N., & Paravastu, Anant K. Evidence for cis Amide Bonds in Peptoid Nanosheets. United States. doi:10.1021/acs.jpclett.8b01040.
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Hudson, Benjamin C., Battigelli, Alessia, Connolly, Michael D., Edison, John, Spencer, Ryan K., Whitelam, Stephen, Zuckermann, Ronald N., and Paravastu, Anant K. Mon . "Evidence for cis Amide Bonds in Peptoid Nanosheets". United States. doi:10.1021/acs.jpclett.8b01040. https://www.osti.gov/servlets/purl/1515161.
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@article{osti_1515161,
title = {Evidence for cis Amide Bonds in Peptoid Nanosheets},
author = {Hudson, Benjamin C. and Battigelli, Alessia and Connolly, Michael D. and Edison, John and Spencer, Ryan K. and Whitelam, Stephen and Zuckermann, Ronald N. and Paravastu, Anant K.},
abstractNote = {Peptoid nanosheets are supramolecular protein-mimetic materials that form from amphiphilic polypeptoids with aromatic and ionic side chains. Nanosheets have been studied at the nanometer scale, but the molecular structure has been difficult to probe. We introduce the use of 13C-13C dipolar recoupling solid-state NMR measurements to reveal the configuration of backbone amide bonds selected by 13C isotopic labeling of adjacent α-carbons. Measurements on the same molecules in the amorphous state and in nanosheets revealed that amide bonds in the center of the amino block of peptoid (NaeNpe)7-(NceNpe)7(B28) favor the trans configuration in the amorphous state and the cis configuration in the nanosheet. This unexpected conclusion contrasts with previous NMR and theoretical studies of short solvated peptoids. Moreover, examination of the amide bond at the junction of the two charged blocks within B28 revealed a mixture of both cis and trans configurational states, consistent with the previously predicted brickwork-like intermolecular organization.},
doi = {10.1021/acs.jpclett.8b01040},
journal = {Journal of Physical Chemistry Letters},
number = 10,
volume = 9,
place = {United States},
year = {2018},
month = {4}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI:  10.1021/acs.jpclett.8b01040
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Citation Metrics:
Cited by: 11 works
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Figures / Tables:

Figure 1 Figure 1: A) and B) Planar representations of a backbone peptoid amide bond in the cis and trans configurations, respectively. C) Primary structure of peptoid B28 with the positively charged amino block colored in blue and the negatively charged carboxylic acid block colored in red.
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Works referencing / citing this record:

Crystallization and lamellar nanosheet formation of an aromatic dipeptoid
journal, January 2019

  • Castelletto, Valeria; Chippindale, Ann M.; Hamley, Ian W.
  • Chemical Communications, Vol. 55, Issue 42
  • DOI: 10.1039/c9cc02335f

Crystallization and lamellar nanosheet formation of an aromatic dipeptoid
journal, January 2019

  • Castelletto, Valeria; Chippindale, Ann M.; Hamley, Ian W.
  • Chemical Communications, Vol. 55, Issue 42
  • DOI: 10.1039/c9cc02335f

Design and preparation of organic nanomaterials using self‐assembled peptoids
journal, February 2019

Stereochemistry of polypeptoid chain configurations
journal, March 2019

  • Spencer, Ryan K.; Butterfoss, Glenn L.; Edison, John R.
  • Biopolymers, Vol. 110, Issue 6
  • DOI: 10.1002/bip.23266

Unconstrained peptoid tetramer exhibits a predominant conformation in aqueous solution
journal, March 2019

  • Roe, Leah T.; Pelton, Jeffrey G.; Edison, John R.
  • Biopolymers, Vol. 110, Issue 6
  • DOI: 10.1002/bip.23267

Recent advances in crystallization and self‐assembly of polypeptoid polymers
journal, June 2019

  • Zeng, Guangjian; Qiu, Lu; Wen, Tao
  • POLYMER CRYSTALLIZATION, Vol. 2, Issue 3
  • DOI: 10.1002/pcr2.10065

A bio-inspired approach to ligand design: folding single-chain peptoids to chelate a multimetallic cluster
journal, January 2018

  • Nguyen, Andy I.; Spencer, Ryan K.; Anderson, Christopher L.
  • Chemical Science, Vol. 9, Issue 47
  • DOI: 10.1039/c8sc04240c

Conformations of peptoids in nanosheets result from the interplay of backbone energetics and intermolecular interactions
journal, May 2018

  • Edison, John R.; Spencer, Ryan K.; Butterfoss, Glenn L.
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 22
  • DOI: 10.1073/pnas.1800397115
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