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Proteins can form homomeric complexes with another unit of the same protein or heteromeric complexes with different types.  Most protein complexes self-assemble spontaneously via ordered pathways, while some proteins need assembly factors that guide their proper assembly. Despite the crowded intracellular environment, proteins usually interact with their correct partners and form functional complexes.
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Assembly and Characterization of Polyelectrolyte Complex Micelles
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Non-equilibrium phenomena and kinetic pathways in self-assembled polyelectrolyte complexes.

Hao Wu1, Jeffrey M Ting1, Olivia Werba2

  • 1Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA.

The Journal of Chemical Physics
|November 3, 2018
PubMed
Summary

Kinetically trapped polyelectrolyte complexes, unlike thermodynamically stable ones, form transient structures. These metastable aggregates evolve over time, offering new insights into non-equilibrium self-assembly for advanced applications.

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Area of Science:

  • Polymer Science
  • Materials Science
  • Physical Chemistry

Background:

  • Polyelectrolyte complexation typically focuses on equilibrium states.
  • Kinetically trapped, non-equilibrium states in polyelectrolyte assemblies are less understood.
  • Understanding these states is crucial for novel material design.

Purpose of the Study:

  • Investigate the structural evolution of non-equilibrium polyelectrolyte aggregates.
  • Compare the impact of different formation pathways (direct dissolution vs. salt annealing).
  • Characterize the transition from metastable to stable states.

Main Methods:

  • Time-resolved dynamic light scattering.
  • Small-angle X-ray scattering (SAXS).
  • Cryogenic transmission electron microscopy (Cryo-TEM).

Main Results:

  • Salt annealing produced kinetically trapped, transient structures, while direct dissolution yielded stable products.
  • Transient aggregates transformed into stable products post-salt addition.
  • Cryo-TEM revealed interconnected morphologies; SAXS indicated fuzzy globular complexes (Rg ~ 10 nm).
  • A two-step transformation process involved aggregate breakdown and redistribution.
  • Aggregate disintegration followed a stretched exponential function, indicating heterogeneity.

Conclusions:

  • Formation pathways significantly influence the structure and stability of polyelectrolyte complexes.
  • Non-equilibrium states exhibit complex morphological evolution and heterogeneity.
  • This study advances the understanding of far-from-equilibrium self-assembly for potential applications.