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:
-
- Georgia Inst. of Technology, Atlanta, GA (United States)
- 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.
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. https://doi.org/10.1021/acs.jpclett.8b01040
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. https://doi.org/10.1021/acs.jpclett.8b01040. https://www.osti.gov/servlets/purl/1515161.
@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}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Free-floating ultrathin two-dimensional crystals from sequence-specific peptoid polymers
journal, April 2010
- Nam, Ki Tae; Shelby, Sarah A.; Choi, Philip H.
- Nature Materials, Vol. 9, Issue 5
Simple, Helical Peptoid Analogs of Lung Surfactant Protein B
journal, January 2005
- Seurynck, Shannon L.; Patch, James A.; Barron, Annelise E.
- Chemistry & Biology, Vol. 12, Issue 1
Helical Peptoid Mimics of Lung Surfactant Protein C
journal, November 2003
- Wu, Cindy W.; Seurynck, Shannon L.; Lee, Ka Yee C.
- Chemistry & Biology, Vol. 10, Issue 11
Design, Synthesis, Assembly, and Engineering of Peptoid Nanosheets
journal, January 2016
- Robertson, Ellen J.; Battigelli, Alessia; Proulx, Caroline
- Accounts of Chemical Research, Vol. 49, Issue 3
Sequence Programmable Peptoid Polymers for Diverse Materials Applications
journal, April 2015
- Knight, Abigail S.; Zhou, Effie Y.; Francis, Matthew B.
- Advanced Materials, Vol. 27, Issue 38
Development and use of an atomistic CHARMM-based forcefield for peptoid simulation
journal, November 2013
- Mirijanian, Dina T.; Mannige, Ranjan V.; Zuckermann, Ronald N.
- Journal of Computational Chemistry, Vol. 35, Issue 5
Kinetics and Equilibria of Cis/Trans Isomerization of Backbone Amide Bonds in Peptoids
journal, October 2007
- Sui, Qiang; Borchardt, Dan; Rabenstein, Dallas L.
- Journal of the American Chemical Society, Vol. 129, Issue 39
Symmetry-based constant-time homonuclear dipolar recoupling in solid state NMR
journal, February 2007
- Tycko, Robert
- The Journal of Chemical Physics, Vol. 126, Issue 6
Peptoid nanosheets exhibit a new secondary-structure motif
journal, October 2015
- Mannige, Ranjan V.; Haxton, Thomas K.; Proulx, Caroline
- Nature, Vol. 526, Issue 7573
Molecular Structure of RADA16-I Designer Self-Assembling Peptide Nanofibers
journal, August 2013
- Cormier, Ashley R.; Pang, Xiaodong; Zimmerman, Maxwell I.
- ACS Nano, Vol. 7, Issue 9
Supramolecular Structure in Full-Length Alzheimer's β-Amyloid Fibrils: Evidence for a Parallel β-Sheet Organization from Solid-State Nuclear Magnetic Resonance
journal, August 2002
- Balbach, John J.; Petkova, Aneta T.; Oyler, Nathan A.
- Biophysical Journal, Vol. 83, Issue 2
Polymorphism in Alzheimer Aβ Amyloid Organization Reflects Conformational Selection in a Rugged Energy Landscape
journal, August 2010
- Miller, Yifat; Ma, Buyong; Nussinov, Ruth
- Chemical Reviews, Vol. 110, Issue 8
Molecular Structures of Amyloid and Prion Fibrils: Consensus versus Controversy
journal, January 2013
- Tycko, Robert; Wickner, Reed B.
- Accounts of Chemical Research, Vol. 46, Issue 7
Self-Assembled Oligoanilinic Nanosheets: Molecular Structure Revealed by Solid-State NMR Spectroscopy
journal, November 2015
- Zujovic, Zoran; Webber, Amy L.; Travas-Sejdic, Jadranka
- Macromolecules, Vol. 48, Issue 24
Structure elucidation of a complex CO 2 -based organic framework material by NMR crystallography
journal, January 2016
- Leclaire, Julien; Poisson, Guillaume; Ziarelli, Fabio
- Chemical Science, Vol. 7, Issue 7
High Field Solid-State NMR Spectroscopy Investigation of 15 N-Labeled Rosette Nanotubes: Hydrogen Bond Network and Channel-Bound Water
journal, May 2016
- Fenniri, Hicham; Tikhomirov, Grigory A.; Brouwer, Darren H.
- Journal of the American Chemical Society, Vol. 138, Issue 19
Folding of xylan onto cellulose fibrils in plant cell walls revealed by solid-state NMR
journal, December 2016
- Simmons, Thomas J.; Mortimer, Jenny C.; Bernardinelli, Oigres D.
- Nature Communications, Vol. 7, Issue 1
Co-existence of Distinct Supramolecular Assemblies in Solution and in the Solid State
journal, December 2016
- Reddy, G. N. Manjunatha; Huqi, Aida; Iuga, Dinu
- Chemistry - A European Journal, Vol. 23, Issue 10
Recoupling of Heteronuclear Dipolar Interactions with Rotational-Echo Double-Resonance at High Magic-Angle Spinning Frequencies
journal, September 2000
- Jaroniec, Christopher P.; Tounge, Brett A.; Rienstra, Chad M.
- Journal of Magnetic Resonance, Vol. 146, Issue 1
SPINEVOLUTION: A powerful tool for the simulation of solid and liquid state NMR experiments
journal, February 2006
- Veshtort, Mikhail; Griffin, Robert G.
- Journal of Magnetic Resonance, Vol. 178, Issue 2
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
Works referencing / citing this record:
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
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
Effect of processing and end groups on the crystal structure of polypeptoids studied by cryogenic electron microscopy at atomic length scales
journal, January 2019
- Jiang, Xi; Xuan, Sunting; Kundu, Joyjit
- Soft Matter, Vol. 15, Issue 23
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
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
Design and preparation of organic nanomaterials using self‐assembled peptoids
journal, February 2019
- Battigelli, Alessia
- Biopolymers, Vol. 110, Issue 4
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
Stereochemistry of polypeptoid chain configurations
journal, March 2019
- Spencer, Ryan K.; Butterfoss, Glenn L.; Edison, John R.
- Biopolymers, Vol. 110, Issue 6
Figures / Tables found in this record: