Chirality-selected phase behaviour in ionic polypeptide complexes

Sarah L. Perry, Lorraine Leon, Kyle Q. Hoffmann, Matthew J. Kade, Dimitrios Priftis, Katie A. Black, Derek Wong, Ryan A. Klein, Charles F. Pierce, Khatcher O. Margossian, Jonathan K. Whitmer, Jian Qin, Juan J. de Pablo and Matthew Tirrell ()
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Sarah L. Perry: Institute for Molecular Engineering, University of Chicago
Lorraine Leon: Institute for Molecular Engineering, University of Chicago
Kyle Q. Hoffmann: Institute for Molecular Engineering, University of Chicago
Matthew J. Kade: Institute for Molecular Engineering, University of Chicago
Dimitrios Priftis: Institute for Molecular Engineering, University of Chicago
Katie A. Black: University of California at Berkeley
Derek Wong: Institute for Molecular Engineering, University of Chicago
Ryan A. Klein: Institute for Molecular Engineering, University of Chicago
Charles F. Pierce: Institute for Molecular Engineering, University of Chicago
Khatcher O. Margossian: Institute for Molecular Engineering, University of Chicago
Jonathan K. Whitmer: Institute for Molecular Engineering, University of Chicago
Jian Qin: Institute for Molecular Engineering, University of Chicago
Juan J. de Pablo: Institute for Molecular Engineering, University of Chicago
Matthew Tirrell: Institute for Molecular Engineering, University of Chicago

Nature Communications, 2015, vol. 6, issue 1, 1-8

Abstract: Abstract 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.

Date: 2015
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DOI: 10.1038/ncomms7052

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