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Title: Non-equilibrium phenomena and kinetic pathways in self-assembled polyelectrolyte complexes

Abstract

Polyelectrolyte complexation has been conventionally focused on the thermodynamic states, where assemblies have equilibrated in solutions. Far less attention has been given to complex systems that are kinetically trapped at non-equilibrium states. A combination of time-resolved dynamic light scattering, small angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (Cryo-TEM) was employed here to investigate the internal structures and morphological evolution of non-equilibrium aggregates forming from a pair of two strong block polyelectrolytes over wide time and length scales. The role of formation pathways of electrostatically driven aggregates was assessed using two processing protocols: direct dissolution and salt annealing. The former led to thermodynamically stable products, while the latter resulted in kinetically trapped transient structures. After adding salt, the metastable structures gradually transformed into stable products. Cryo-TEM images showed the interconnected irregular morphologies of the aggregates, and SAXS data revealed the presence of fuzzy globular complexes with R-g similar to 10 nm within them. A two-step process in the time-dependent structural transformation was found and characterized by a fast breakdown of interconnected transient aggregates followed by a slow redistribution of the incipient individual electrostatic assemblies. Furthermore, the prolonged aggregate disintegration process fitting to a stretched exponential function unveiled the broadmore » relaxation distribution and significant structural heterogeneity in these polyelectrolyte complex nanoaggregates. This work brings new insight into the comprehension of non-equilibrium phenomena in self-assembled electrostatic assemblies and represents a first step toward constructing far-from-equilibrium polyelectrolyte complexes de novo for future applications.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [3];  [1]
  1. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Chicago, IL (United States). Dept. of Chemistry
  3. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Institute of Standards and Technology (NIST)
OSTI Identifier:
1490235
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wu, Hao, Ting, Jeffrey M., Werba, Olivia, Meng, Siqi, and Tirrell, Matthew V. Non-equilibrium phenomena and kinetic pathways in self-assembled polyelectrolyte complexes. United States: N. p., 2018. Web. doi:10.1063/1.5039621.
Wu, Hao, Ting, Jeffrey M., Werba, Olivia, Meng, Siqi, & Tirrell, Matthew V. Non-equilibrium phenomena and kinetic pathways in self-assembled polyelectrolyte complexes. United States. https://doi.org/10.1063/1.5039621
Wu, Hao, Ting, Jeffrey M., Werba, Olivia, Meng, Siqi, and Tirrell, Matthew V. Mon . "Non-equilibrium phenomena and kinetic pathways in self-assembled polyelectrolyte complexes". United States. https://doi.org/10.1063/1.5039621. https://www.osti.gov/servlets/purl/1490235.
@article{osti_1490235,
title = {Non-equilibrium phenomena and kinetic pathways in self-assembled polyelectrolyte complexes},
author = {Wu, Hao and Ting, Jeffrey M. and Werba, Olivia and Meng, Siqi and Tirrell, Matthew V.},
abstractNote = {Polyelectrolyte complexation has been conventionally focused on the thermodynamic states, where assemblies have equilibrated in solutions. Far less attention has been given to complex systems that are kinetically trapped at non-equilibrium states. A combination of time-resolved dynamic light scattering, small angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (Cryo-TEM) was employed here to investigate the internal structures and morphological evolution of non-equilibrium aggregates forming from a pair of two strong block polyelectrolytes over wide time and length scales. The role of formation pathways of electrostatically driven aggregates was assessed using two processing protocols: direct dissolution and salt annealing. The former led to thermodynamically stable products, while the latter resulted in kinetically trapped transient structures. After adding salt, the metastable structures gradually transformed into stable products. Cryo-TEM images showed the interconnected irregular morphologies of the aggregates, and SAXS data revealed the presence of fuzzy globular complexes with R-g similar to 10 nm within them. A two-step process in the time-dependent structural transformation was found and characterized by a fast breakdown of interconnected transient aggregates followed by a slow redistribution of the incipient individual electrostatic assemblies. Furthermore, the prolonged aggregate disintegration process fitting to a stretched exponential function unveiled the broad relaxation distribution and significant structural heterogeneity in these polyelectrolyte complex nanoaggregates. This work brings new insight into the comprehension of non-equilibrium phenomena in self-assembled electrostatic assemblies and represents a first step toward constructing far-from-equilibrium polyelectrolyte complexes de novo for future applications.},
doi = {10.1063/1.5039621},
journal = {Journal of Chemical Physics},
number = 16,
volume = 149,
place = {United States},
year = {Mon Jul 30 00:00:00 EDT 2018},
month = {Mon Jul 30 00:00:00 EDT 2018}
}

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