title: Chirality-selected phase behaviour in ionic polypeptide complexes.
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.
authors.affiliation: Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Sarah L
authors.initials: SL
authors.lastname: Perry
authors.affiliation: 1] Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA [2] Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: Lorraine
authors.initials: L
authors.lastname: Leon
authors.affiliation: 1] Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA [2] Department of Chemical Engineering, University of Wisconsin, Madison, Wisconsin 53706, USA.
authors.forename: Kyle Q
authors.initials: KQ
authors.lastname: Hoffmann
authors.affiliation: 1] Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA [2] Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Kade
authors.affiliation: Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Dimitrios
authors.initials: D
authors.lastname: Priftis
authors.affiliation: Department of Bioengineering, University of California at Berkeley, Berkeley, California 94720, USA.
authors.forename: Katie A
authors.initials: KA
authors.lastname: Black
authors.affiliation: Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Derek
authors.initials: D
authors.lastname: Wong
authors.affiliation: Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Ryan A
authors.initials: RA
authors.lastname: Klein
authors.affiliation: Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Charles F
authors.initials: CF
authors.lastname: Pierce
authors.affiliation: Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Khatcher O
authors.initials: KO
authors.lastname: Margossian
authors.affiliation: 1] Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA [2] Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: Jonathan K
authors.initials: JK
authors.lastname: Whitmer
authors.affiliation: Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Jian
authors.initials: J
authors.lastname: Qin
authors.affiliation: 1] Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA [2] Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: Juan J
authors.initials: JJ
authors.lastname: de Pablo
authors.affiliation: 1] Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA [2] Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: Matthew
authors.initials: M
authors.lastname: Tirrell
mesh_terms: D006860:Hydrogen Bonding; D010455:Peptides / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D017433:Protein Structure, Secondary; D013237:Stereoisomerism
chemical_list: D010455:Peptides; D011108:Polymers