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

Wu, Hao; Ting, Jeffrey M.; Werba, Olivia; Meng, Siqi; Tirrell, Matthew V.

doi:10.1063/1.5039621

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

Journal Article · Mon Jul 30 00:00:00 EDT 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5039621· OSTI ID:1490235

^[1];

^[1]; Werba, Olivia ^[2];

^[3]; Tirrell, Matthew V. ^[1]

Univ. of Chicago, IL (United States). Inst. for Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Chicago, IL (United States). Dept. of Chemistry
Univ. of Chicago, IL (United States). Inst. for Molecular Engineering

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Institute of Standards and Technology (NIST)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1490235

Journal Information:: Journal of Chemical Physics, Vol. 149, Issue 16; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 31 works

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