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Title: Chirality-selected phase behaviour in ionic polypeptide complexes

Abstract

In this study, polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with a β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.

Authors:
 [1];  [2];  [3];  [2];  [1];  [4];  [1];  [1];  [1];  [1];  [2];  [1];  [2];  [2]
  1. Univ. of Chicago, Chicago, IL (United States)
  2. Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of Chicago, Chicago, IL (United States); Univ. of Wisconsin, Madison, WI (United States)
  4. Univ. of California at Berkeley, Berkeley, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Materials Sciences and Engineering Division
OSTI Identifier:
1225228
Alternate Identifier(s):
OSTI ID: 1352851
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; chemical sciences; condensed matter; materials science; physical chemistry; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Perry, Sarah L., Leon, Lorraine, Hoffmann, Kyle Q., Kade, Matthew J., Priftis, Dimitrios, Black, Katie A., Wong, Derek, Klein, Ryan A., Pierce, III, Charles F., Margossian, Khatcher O., Whitmer, Jonathan K., Qin, Jian, de Pablo, Juan J., and Tirrell, Matthew. Chirality-selected phase behaviour in ionic polypeptide complexes. United States: N. p., 2015. Web. doi:10.1038/ncomms7052.
Perry, Sarah L., Leon, Lorraine, Hoffmann, Kyle Q., Kade, Matthew J., Priftis, Dimitrios, Black, Katie A., Wong, Derek, Klein, Ryan A., Pierce, III, Charles F., Margossian, Khatcher O., Whitmer, Jonathan K., Qin, Jian, de Pablo, Juan J., & Tirrell, Matthew. Chirality-selected phase behaviour in ionic polypeptide complexes. United States. doi:10.1038/ncomms7052.
Perry, Sarah L., Leon, Lorraine, Hoffmann, Kyle Q., Kade, Matthew J., Priftis, Dimitrios, Black, Katie A., Wong, Derek, Klein, Ryan A., Pierce, III, Charles F., Margossian, Khatcher O., Whitmer, Jonathan K., Qin, Jian, de Pablo, Juan J., and Tirrell, Matthew. Wed . "Chirality-selected phase behaviour in ionic polypeptide complexes". United States. doi:10.1038/ncomms7052. https://www.osti.gov/servlets/purl/1225228.
@article{osti_1225228,
title = {Chirality-selected phase behaviour in ionic polypeptide complexes},
author = {Perry, Sarah L. and Leon, Lorraine and Hoffmann, Kyle Q. and Kade, Matthew J. and Priftis, Dimitrios and Black, Katie A. and Wong, Derek and Klein, Ryan A. and Pierce, III, Charles F. and Margossian, Khatcher O. and Whitmer, Jonathan K. and Qin, Jian and de Pablo, Juan J. and Tirrell, Matthew},
abstractNote = {In this study, polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with a β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.},
doi = {10.1038/ncomms7052},
journal = {Nature Communications},
number = ,
volume = 6,
place = {United States},
year = {2015},
month = {1}
}

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