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Title: Chirality-selected phase behaviour in ionic polypeptide complexes

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms7052· OSTI ID:1225228
 [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)

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 beta-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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Materials Sciences and Engineering Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1225228
Alternate ID(s):
OSTI ID: 1352851
Journal Information:
Nature Communications, Vol. 6; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 206 works
Citation information provided by
Web of Science

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Cited By (28)

Biomolecular Chemistry in Liquid Phase Separated Compartments journal April 2019
Phase transitions as intermediate steps in the formation of molecularly engineered protein fibers journal July 2018
Of Thiols and Disulfides: Methods for Chemoselective Formation of Asymmetric Disulfides in Synthetic Peptides and Polymers journal July 2018
Mapping the phase behavior of coacervate-driven self-assembly in diblock copolyelectrolytes journal January 2019
Charge Correlations for Precise, Coulombically Driven Self Assembly journal November 2015
Micro- to macro-phase separation transition in sequence-defined coacervates journal January 2020
Polyelectrolyte complex coacervation by electrostatic dipolar interactions journal October 2018
Effect of polydiacetylene-based nanosomes on cell viability and endocytosis journal April 2019
Non-equilibrium phenomena and kinetic pathways in self-assembled polyelectrolyte complexes journal October 2018
Zigzag‐Helix Transformation of Expanded Polyvaline Induced by Racemization journal August 2019
Tardigrade inspired polyelectrolyte complexation and functional materials journal January 2019
Secondary structures in synthetic polypeptides from N -carboxyanhydrides: design, modulation, association, and material applications journal January 2018
Mesquite gum/chitosan insoluble complexes: relationship between the water state and viscoelastic properties journal October 2018
Intrinsically disordered proteins access a range of hysteretic phase separation behaviors journal October 2019
A Robust Salty Water Adhesive by Counterion Exchange Induced Coacervate journal January 2019
Complexation and coacervation of like-charged polyelectrolytes inspired by mussels journal February 2016
Macro- and Microphase Separated Protein-Polyelectrolyte Complexes: Design Parameters and Current Progress journal March 2019
Condensates of short peptides and ATP for the temporal regulation of cytochrome c activity journal January 2019
Dynamic Synthetic Cells Based on Liquid–Liquid Phase Separation journal August 2019
Structural transitions and encapsulation selectivity of thermoresponsive polyelectrolyte complex micelles journal January 2019
A molecular view of the role of chirality in charge-driven polypeptide complexation journal January 2015
Engineering Peptide-Based Polyelectrolyte Complexes with Increased Hydrophobicity journal March 2019
Underwater contact adhesion and microarchitecture in polyelectrolyte complexes actuated by solvent exchange journal January 2016
Rigidity Rules in DNA Droplets: Nucleic Acid Flexibility Affects Model Membraneless Organelles journal November 2018
Tunable Coacervation of Well-Defined Homologous Polyanions and Polycations by Local Polarity journal February 2019
Designing Electrostatic Interactions via Polyelectrolyte Monomer Sequence journal March 2019
Sequence and entropy-based control of complex coacervates journal November 2017
Upper Critical Solution Temperature (UCST) Behavior of Coacervate of Cationic Protamine and Multivalent Anions journal April 2019

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