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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 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.

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 Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Materials Sciences and Engineering Division
OSTI Identifier:
1225228
Alternate Identifier(s):
OSTI ID: 1352851
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: 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. https://doi.org/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. 2015. "Chirality-selected phase behaviour in ionic polypeptide complexes". United States. https://doi.org/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 = {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.},
doi = {10.1038/ncomms7052},
url = {https://www.osti.gov/biblio/1225228}, journal = {Nature Communications},
issn = {2041-1723},
number = ,
volume = 6,
place = {United States},
year = {Wed Jan 14 00:00:00 EST 2015},
month = {Wed Jan 14 00:00:00 EST 2015}
}

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Cited by: 206 works
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Works referenced in this record:

Analysis of Macromolecular Polydispersity in Intensity Correlation Spectroscopy: The Method of Cumulants
journal, December 1972


Vibrational Energy and Molecular Thermometers in Liquids: Ultrafast IR-Raman Spectroscopy
book, March 2013


P bodies: at the crossroads of post-transcriptional pathways
journal, January 2007


Interfacial Tension of Polyelectrolyte Complex Coacervate Phases
journal, May 2014


Binodal Compositions of Polyelectrolyte Complexes
journal, August 2010


Aqueous Phase Separation as a Possible Route to Compartmentalization of Biological Molecules
journal, February 2012


GROMACS 4:  Algorithms for Highly Efficient, Load-Balanced, and Scalable Molecular Simulation
journal, February 2008


Polyelectrolyte complexes: Bulk phases and colloidal systems
journal, September 2011


The Diastereomeric Assembly of Polylysine Is the Low-Volume Pathway for Preferential Formation of β-Sheet Aggregates
journal, March 2004


Viscosity and interfacial properties in a mussel-inspired adhesive coacervate
journal, January 2010


Peptide–nucleotide microdroplets as a step towards a membrane-free protocell model
journal, August 2011


Complexation and coacervation of polyelectrolytes with oppositely charged colloids
journal, September 2011


Anisotropic domain growth and complex coacervation in nanoclay-polyelectrolyte solutions
journal, September 2011


Kinetics of Aspartic Acid Isomerization and Enantiomerization in Model Aspartyl Tripeptides under Forced Conditions
journal, October 2010


The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes
journal, June 2014


Effects of Polymer and Salt Concentration on the Structure and Properties of Triblock Copolymer Coacervate Hydrogels
journal, February 2013


The Polyelectrolyte Complex/Coacervate Continuum
journal, April 2014


Ternary, Tunable Polyelectrolyte Complex Fluids Driven by Complex Coacervation
journal, April 2014


Injectable fibroblast growth factor-2 coacervate for persistent angiogenesis
journal, August 2011


Flavour encapsulation and controlled release - a review
journal, January 2006


How Robust Are Protein Folding Simulations with Respect to Force Field Parameterization?
journal, May 2011


Beyond Oil and Water--Phase Transitions in Cells
journal, August 2012


Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems
journal, June 1993


Interfacial Energy of Polypeptide Complex Coacervates Measured via Capillary Adhesion
journal, May 2012


Complex coacervate core micelles
journal, March 2009


Synthesis of Thermo- and pH-Sensitive Polyion Complex Micelles for Fluorescent Imaging
journal, January 2012


Thermodynamic Characterization of Polypeptide Complex Coacervation
journal, October 2012


Tunable, High Modulus Hydrogels Driven by Ionic Coacervation
journal, April 2011


Computed circular dichroism spectra for the evaluation of protein conformation
journal, October 1969


Anatomy of energetic changes accompanying urea-induced protein denaturation
journal, September 2007


Polymorphic transitions in single crystals: A new molecular dynamics method
journal, December 1981


General Method for Purification of α-Amino acid- N -carboxyanhydrides Using Flash Chromatography
journal, December 2010


Micellar interpolyelectrolyte complexes
journal, January 2012


Complex coacervation of proteins and anionic polysaccharides
journal, December 2004


Structure and Dynamics of Polyelectrolyte Complex Coacervates Studied by Scattering of Neutrons, X-rays, and Light
journal, May 2013


Determination of Alkali and Halide Monovalent Ion Parameters for Use in Explicitly Solvated Biomolecular Simulations
journal, July 2008


Precipitates withβ-Pleated Sheet Structure by Mixing Aqueous Solutions of Helical Poly(D-lysine) and Poly(L-lysine)
journal, July 1987


Implementation of the CHARMM Force Field in GROMACS: Analysis of Protein Stability Effects from Correction Maps, Virtual Interaction Sites, and Water Models
journal, January 2010


On the Stability and Morphology of Complex Coacervate Core Micelles: From Spherical to Wormlike Micelles
journal, September 2012


Nano- and micro-structured assemblies for encapsulation of food ingredients
journal, January 2009


Phase behaviour and complex coacervation of aqueous polypeptide solutions
journal, January 2012


Relaxation Dynamics at Different Time Scales in Electrostatic Complexes: Time-Salt Superposition
journal, November 2010


Biopolymer stereocomplexes
journal, April 2003


Correction: Phase behaviour and complex coacervation of aqueous polypeptide solutions
journal, January 2015


Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985


LINCS: A linear constraint solver for molecular simulations
journal, September 1997


Improving the specificity of organophosphorus hydrolase to acephate by mutagenesis at its binding site: a computational study
journal, May 2021


Differential Regulation of Single Microtubules and Bundles by a Three-Protein Module
journal, April 2021


Micellar interpolyelectrolyte complexes
text, January 2012


Tunable, High Modulus Hydrogels Driven by Ionic Coacervation
journal, April 2011


Precipitates withβ-Pleated Sheet Structure by Mixing Aqueous Solutions of Helical Poly(D-lysine) and Poly(L-lysine)
journal, July 1987


Synthesis of Thermo- and pH-Sensitive Polyion Complex Micelles for Fluorescent Imaging
journal, January 2012


Kinetics of Aspartic Acid Isomerization and Enantiomerization in Model Aspartyl Tripeptides under Forced Conditions
journal, October 2010


How Robust Are Protein Folding Simulations with Respect to Force Field Parameterization?
journal, May 2011


Complex coacervate core micelles
journal, March 2009


Complex coacervation of proteins and anionic polysaccharides
journal, December 2004


Aqueous Phase Separation as a Possible Route to Compartmentalization of Biological Molecules
journal, February 2012


General Method for Purification of α-Amino acid- N -carboxyanhydrides Using Flash Chromatography
journal, December 2010


Implementation of the CHARMM Force Field in GROMACS: Analysis of Protein Stability Effects from Correction Maps, Virtual Interaction Sites, and Water Models
journal, January 2010


The Diastereomeric Assembly of Polylysine Is the Low-Volume Pathway for Preferential Formation of β-Sheet Aggregates
journal, March 2004


Interfacial Energy of Polypeptide Complex Coacervates Measured via Capillary Adhesion
journal, May 2012


On the Stability and Morphology of Complex Coacervate Core Micelles: From Spherical to Wormlike Micelles
journal, September 2012


Ternary, Tunable Polyelectrolyte Complex Fluids Driven by Complex Coacervation
journal, April 2014


Peptide–nucleotide microdroplets as a step towards a membrane-free protocell model
journal, August 2011


Viscosity and interfacial properties in a mussel-inspired adhesive coacervate
journal, January 2010


Injectable fibroblast growth factor-2 coacervate for persistent angiogenesis
journal, August 2011


Micellar interpolyelectrolyte complexes
text, January 2012


Works referencing / citing this record:

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


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


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


Intrinsically disordered proteins access a range of hysteretic phase separation behaviors
journal, October 2019


Engineering Peptide-Based Polyelectrolyte Complexes with Increased Hydrophobicity
journal, March 2019


Macro- and Microphase Separated Protein-Polyelectrolyte Complexes: Design Parameters and Current Progress
journal, March 2019