Chirality-selected phase behaviour in ionic polypeptide complexes

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...

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Bibliographic Details
Published in:Nature communications 2015-01, Vol.6 (1), p.6052-6052, Article 6052
Main Authors: Perry, Sarah L., Leon, Lorraine, Hoffmann, Kyle Q., Kade, Matthew J., Priftis, Dimitrios, Black, Katie A., Wong, Derek, Klein, Ryan A., Pierce, Charles F., Margossian, Khatcher O., Whitmer, Jonathan K., Qin, Jian, de Pablo, Juan J., Tirrell, Matthew
Format: Article
Language:English
Subjects:
639/301/119/1002
639/638/403/935
639/638/440/56
639/638/455/959
chemical sciences
condensed matter
Humanities and Social Sciences
Hydrogen Bonding
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
MATERIALS SCIENCE
multidisciplinary
Peptides - chemistry
physical chemistry
Polymers - chemistry
Protein Structure, Secondary
Science
Science (multidisciplinary)
Stereoisomerism
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Summary: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. Complexes that form between oppositely charged polyelectrolytes may be solid or liquid. Here, Perry et al. show that chirality in polypeptides can determine the state of those complexes based on a propensity for hydrogen-bond formation.
ISSN:2041-1723
2041-1723
DOI:10.1038/ncomms7052