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 »
- Authors:
-
- 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
- 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}
}
Web of Science
Works referenced in this record:
Prediction of temperature-dependent free recovery behaviors of amorphous shape memory polymers
journal, January 2012
- Ge, Qi; Yu, Kai; Ding, Yifu
- Soft Matter, Vol. 8, Issue 43
On the origin of the non-exponential behaviour of the -relaxation in glass-forming polymers: incoherent neutron scattering and dielectric relaxation results
journal, January 1999
- Colmenero, J.; Arbe, A.; Alegría, A.
- Journal of Physics: Condensed Matter, Vol. 11, Issue 10A
Poly(vinyl benzyl trimethylammonium chloride) Homo and Block Copolymers Complexation with DNA
journal, February 2016
- Haladjova, Emi; Mountrichas, Grigoris; Pispas, Stergios
- The Journal of Physical Chemistry B, Vol. 120, Issue 9
Dynamics of associative polymers
journal, January 2018
- Zhang, Zhijie; Chen, Quan; Colby, Ralph H.
- Soft Matter, Vol. 14, Issue 16
Functional Materials Based on Self-Assembly of Polymeric Supramolecules
journal, March 2002
- Ikkala, O.
- Science, Vol. 295, Issue 5564
Kinetic Control over Pathway Complexity in Supramolecular Polymerization through Modulating the Energy Landscape by Rational Molecular Design
journal, October 2014
- Ogi, Soichiro; Fukui, Tomoya; Jue, Melinda L.
- Angewandte Chemie International Edition, Vol. 53, Issue 52
Redistribution of Block Copolymer Chains between Mixed Micelles in Solution
journal, July 1998
- Esselink, F. J.; Dormidontova, E. E.; Hadziioannou, G.
- Macromolecules, Vol. 31, Issue 15
Complex Coacervation Core Micelles. Colloidal Stability and Aggregation Mechanism
journal, February 2004
- van der Burgh, Stefan; de Keizer, Arie; Cohen Stuart, Martien A.
- Langmuir, Vol. 20, Issue 4
Stability of Complex Coacervate Core Micelles Containing Metal Coordination Polymer
journal, September 2008
- Yan, Yun; de Keizer, Arie; Cohen Stuart, Martien A.
- The Journal of Physical Chemistry B, Vol. 112, Issue 35
Structural Observation and Kinetic Pathway in the Formation of Polymeric Micelles
journal, May 2009
- Lund, Reidar; Willner, Lutz; Monkenbusch, Michael
- Physical Review Letters, Vol. 102, Issue 18
Molecular and structural basis of low interfacial energy of complex coacervates in water
journal, January 2017
- Jho, YongSeok; Yoo, Hee Young; Lin, Yanxian
- Advances in Colloid and Interface Science, Vol. 239
Identification of the platelet ADP receptor targeted by antithrombotic drugs
journal, January 2001
- Hollopeter, Gunther; Jantzen, Hans-Michael; Vincent, Diana
- Nature, Vol. 409, Issue 6817
Regularized Positive Exponential Sum (REPES) Program - A Way of Inverting Laplace Transform Data Obtained by Dynamic Light Scattering
journal, January 1995
- Jakeš, Jaromír
- Collection of Czechoslovak Chemical Communications, Vol. 60, Issue 11
Dynamics of Glass-Forming Polymers: “Homogeneous” versus “Heterogeneous” Scenario
journal, July 1998
- Arbe, A.; Colmenero, J.; Monkenbusch, M.
- Physical Review Letters, Vol. 81, Issue 3
The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes
journal, June 2014
- Perry, Sarah; Li, Yue; Priftis, Dimitrios
- Polymers, Vol. 6, Issue 6
Crystallization-induced switching of the morphology of poly(ethylene oxide)-block-polybutadiene micelles
journal, January 2009
- Mihut, Adriana M.; Chiche, Arnaud; Drechsler, Markus
- Soft Matter, Vol. 5, Issue 1
Improved techniques for particle size determination by quasi-elastic light scattering
journal, July 1985
- Morrison, Ian D.; Grabowski, E. F.; Herb, C. A.
- Langmuir, Vol. 1, Issue 4
Interpolyelectrolyte Complexes of Polycationic Micelles and Linear Polyanions: Structural Stability and Temporal Evolution
journal, December 2015
- Laaser, Jennifer E.; Jiang, Yaming; Petersen, Shannon R.
- The Journal of Physical Chemistry B, Vol. 119, Issue 52
Polyion Complex Nanomaterials from Block Polyelectrolyte Micelles and Linear Polyelectrolytes of Opposite Charge. 2. Dynamic Properties
journal, July 2008
- Chelushkin, Pavel S.; Lysenko, Evgeny A.; Bronich, Tatiana K.
- The Journal of Physical Chemistry B, Vol. 112, Issue 26
Kinetic Products in Coordination Networks: Ab Initio X-ray Powder Diffraction Analysis
journal, December 2012
- Martí-Rujas, Javier; Kawano, Masaki
- Accounts of Chemical Research, Vol. 46, Issue 2
Small-Angle Scattering from Polymeric Mass Fractals of Arbitrary Mass-Fractal Dimension
journal, April 1996
- Beaucage, G.
- Journal of Applied Crystallography, Vol. 29, Issue 2
The history of the stretched exponential function
journal, December 2007
- Cardona, M.; Chamberlin, R. V.; Marx, W.
- Annalen der Physik, Vol. 16, Issue 12
Reversibility and Relaxation Behavior of Polyelectrolyte Complex Micelle Formation
journal, April 2009
- Lindhoud, Saskia; Norde, Willem; Cohen Stuart, Martien A.
- The Journal of Physical Chemistry B, Vol. 113, Issue 16
Self-assembly in synthetic macromolecular systems via multiple hydrogen bonding interactions
journal, January 2001
- Sherrington, David C.; Taskinen, Kirsti A.
- Chemical Society Reviews, Vol. 30, Issue 2
Supramolecular Interactions in Chemomechanical Polymers
journal, October 2009
- Schneider, Hans-Jörg; Strongin, Robert M.
- Accounts of Chemical Research, Vol. 42, Issue 10
Direct observation of kinetic traps associated with structural transformations leading to multiple pathways of S-layer assembly
journal, July 2012
- Shin, S. -H.; Chung, S.; Sanii, B.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 32
Self-Assembly of Block Copolymer Micelles in an Ionic Liquid
journal, March 2006
- He, Yiyong; Li, Zhibo; Simone, Peter
- Journal of the American Chemical Society, Vol. 128, Issue 8
Origin of translocation barriers for polyelectrolyte chains
journal, January 2009
- Kumar, Rajeev; Muthukumar, M.
- The Journal of Chemical Physics, Vol. 131, Issue 19
Ternary, Tunable Polyelectrolyte Complex Fluids Driven by Complex Coacervation
journal, April 2014
- Priftis, Dimitrios; Xia, Xiaoxing; Margossian, Khatcher O.
- Macromolecules, Vol. 47, Issue 9
Evidence of a two-step process and pathway dependency in the thermodynamics of poly(diallyldimethylammonium chloride)/poly(sodium acrylate) complexation
journal, January 2014
- Vitorazi, L.; Ould-Moussa, N.; Sekar, S.
- Soft Matter, Vol. 10, Issue 47
Phase separation in polyelectrolyte solutions. Theory of complex coacervation
journal, May 1957
- Overbeek, J. T. G.; Voorn, M. J.
- Journal of Cellular and Comparative Physiology, Vol. 49, Issue S1
Anomalous Self-Diffusion and Sticky Rouse Dynamics in Associative Protein Hydrogels
journal, March 2015
- Tang, Shengchang; Wang, Muzhou; Olsen, Bradley D.
- Journal of the American Chemical Society, Vol. 137, Issue 11
Complex coacervates based on recombinant mussel adhesive proteins: their characterization and applications
journal, January 2017
- Kim, Hyo Jeong; Yang, Byeongseon; Park, Tae Yoon
- Soft Matter, Vol. 13, Issue 42
Self-assembly via microfluidics
journal, January 2015
- Wang, Lei; Sánchez, Samuel
- Lab on a Chip, Vol. 15, Issue 23
Size evolution of highly amphiphilic macromolecular solution assemblies via a distinct bimodal pathway
journal, April 2014
- Kelley, Elizabeth G.; Murphy, Ryan P.; Seppala, Jonathan E.
- Nature Communications, Vol. 5, Issue 1
Living supramolecular polymerization realized through a biomimetic approach
journal, February 2014
- Ogi, Soichiro; Sugiyasu, Kazunori; Manna, Swarup
- Nature Chemistry, Vol. 6, Issue 3
50th Anniversary Perspective : A Perspective on Polyelectrolyte Solutions
journal, December 2017
- Muthukumar, M.
- Macromolecules, Vol. 50, Issue 24
Non-equilibrium ionic assemblies of oppositely charged nanoparticles
journal, January 2013
- Zhang, Rui; Jha, Prateek K.; Olvera de la Cruz, Monica
- Soft Matter, Vol. 9, Issue 20
Phase Behavior and Salt Partitioning in Polyelectrolyte Complex Coacervates
journal, April 2018
- Li, Lu; Srivastava, Samanvaya; Andreev, Marat
- Macromolecules, Vol. 51, Issue 8
Structure and Stability of Complex Coacervate Core Micelles with Lysozyme
journal, July 2007
- Lindhoud, Saskia; de Vries, Renko; Norde, Willem
- Biomacromolecules, Vol. 8, Issue 7
Complexation of DNA with Cationic Copolymer Micelles: Effects of DNA Length and Topology
journal, February 2018
- Jiang, Yaming; Reineke, Theresa M.; Lodge, Timothy P.
- Macromolecules, Vol. 51, Issue 3
Dynamics of Glass Relaxation at Room Temperature
journal, June 2013
- Welch, Roger C.; Smith, John R.; Potuzak, Marcel
- Physical Review Letters, Vol. 110, Issue 26
Experimental Binding Energies in Supramolecular Complexes
journal, May 2016
- Biedermann, Frank; Schneider, Hans-Jörg
- Chemical Reviews, Vol. 116, Issue 9
Structure and Charge Distribution in DNA and Poly(styrenesulfonate) Aqueous Solutions
journal, May 1997
- Kassapidou, K.; Jesse, W.; Kuil, M. E.
- Macromolecules, Vol. 30, Issue 9
Kinetic trapping – a strategy for directing the self-assembly of unique functional nanostructures
journal, January 2016
- Yan, Yun; Huang, Jianbin; Tang, Ben Zhong
- Chemical Communications, Vol. 52, Issue 80
Irena : tool suite for modeling and analysis of small-angle scattering
journal, February 2009
- Ilavsky, Jan; Jemian, Peter R.
- Journal of Applied Crystallography, Vol. 42, Issue 2
Evolution of hierarchical structures in polyelectrolyte–micelle coacervates
journal, January 2013
- Kizilay, Ebru; Dinsmore, Anthony D.; Hoagland, David A.
- Soft Matter, Vol. 9, Issue 30
Synthesis and Assembly of Designer Styrenic Diblock Polyelectrolytes
journal, May 2018
- Ting, Jeffrey M.; Wu, Hao; Herzog-Arbeitman, Abraham
- ACS Macro Letters, Vol. 7, Issue 6
A review of the early development of the thermodynamics of the complex coacervation phase separation
journal, September 2011
- Veis, Arthur
- Advances in Colloid and Interface Science, Vol. 167, Issue 1-2
Self-Assembly of Ultralong Polyion Nanoladders Facilitated by Ionic Recognition and Molecular Stiffness
journal, January 2014
- Xu, Limin; Jiang, Lingxiang; Drechsler, Markus
- Journal of the American Chemical Society, Vol. 136, Issue 5
Complex coacervate core micelles
journal, March 2009
- Voets, Ilja K.; de Keizer, Arie; Cohen Stuart, Martien A.
- Advances in Colloid and Interface Science, Vol. 147-148
Threading synthetic polyelectrolytes through protein pores
journal, February 2007
- Murphy, Ryan J.; Muthukumar, M.
- The Journal of Chemical Physics, Vol. 126, Issue 5
Visualizing Ribosome Biogenesis: Parallel Assembly Pathways for the 30 S Subunit
journal, October 2010
- Mulder, Anke M.; Yoshioka, Craig; Beck, Andrea H.
- Science, Vol. 330, Issue 6004
Thermodynamic Characterization of Polypeptide Complex Coacervation
journal, October 2012
- Priftis, Dimitrios; Laugel, Nicolas; Tirrell, Matthew
- Langmuir, Vol. 28, Issue 45
Chirality-selected phase behaviour in ionic polypeptide complexes
journal, January 2015
- Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.
- Nature Communications, Vol. 6, Issue 1
Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium and non-equilibrium conditions
journal, September 2009
- Mann, Stephen
- Nature Materials, Vol. 8, Issue 10
SANS from Polymers—Review of the Recent Literature
journal, February 2010
- Hammouda, Boualem
- Polymer Reviews, Vol. 50, Issue 1
Transient network topology of interconnected polyelectrolyte complex micelles
journal, January 2011
- Lemmers, Marc; Voets, Ilja K.; Cohen Stuart, Martien A.
- Soft Matter, Vol. 7, Issue 4
Structure and rheology of polyelectrolyte complex coacervates
journal, January 2018
- Marciel, Amanda B.; Srivastava, Samanvaya; Tirrell, Matthew V.
- Soft Matter, Vol. 14, Issue 13
Tuning Cationic Block Copolymer Micelle Size by pH and Ionic Strength
journal, August 2016
- Sprouse, Dustin; Jiang, Yaming; Laaser, Jennifer E.
- Biomacromolecules, Vol. 17, Issue 9
Pathway complexity in supramolecular polymerization
journal, January 2012
- Korevaar, Peter A.; George, Subi J.; Markvoort, Albert J.
- Nature, Vol. 481, Issue 7382
Chain conformation of linear polyelectrolyte in salt solutions: sodium poly(styrenesulfonate) in potassium chloride and sodium chloride
journal, December 1988
- Wang, Lixiao; Yu, Hyuk
- Macromolecules, Vol. 21, Issue 12
Molecular engineering solutions for therapeutic peptide delivery
journal, January 2017
- Acar, Handan; Ting, Jeffrey M.; Srivastava, Samanvaya
- Chemical Society Reviews, Vol. 46, Issue 21
Controlled mixing of lanthanide(iii) ions in coacervate core micelles
journal, January 2013
- Wang, Junyou; Velders, Aldrik H.; Gianolio, Eliana
- Chemical Communications, Vol. 49, Issue 36
Development of the modern theory of polymeric complex coacervation
journal, January 2017
- Sing, Charles E.
- Advances in Colloid and Interface Science, Vol. 239
Kinetic and thermodynamic processes of organic species at the solution–solid interface: the view through an STM
journal, January 2015
- Mazur, Ursula; Hipps, K. W.
- Chemical Communications, Vol. 51, Issue 23
On the Stability and Morphology of Complex Coacervate Core Micelles: From Spherical to Wormlike Micelles
journal, September 2012
- van der Kooij, Hanne M.; Spruijt, Evan; Voets, Ilja K.
- Langmuir, Vol. 28, Issue 40
Mechanisms of Protein Fibril Formation: Nucleated Polymerization with Competing Off-Pathway Aggregation
journal, January 2008
- Powers, Evan T.; Powers, David L.
- Biophysical Journal, Vol. 94, Issue 2
Controlled mixing of lanthanide(III) ions in coacervate core micelles
text, January 2013
- Wang, Junyou; Velders, Aldrik H.; Gianolio, Eliana
- University of Bayreuth
Kinetic Control over Pathway Complexity in Supramolecular Polymerization through Modulating the Energy Landscape by Rational Molecular Design
journal, October 2014
- Ogi, Soichiro; Fukui, Tomoya; Jue, Melinda L.
- Angewandte Chemie, Vol. 126, Issue 52
Evidence of a two-step process and pathway dependency in the thermodynamics of poly(diallyldimethylammonium chloride)/poly(sodium acrylate) complexation
text, January 2014
- Vitorazi, L.; Ould-Moussa, N.; Sekar, S.
- arXiv
Works referencing / citing this record:
Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks
journal, January 2019
- van Hees, I. A.; Swinkels, P. J. M.; Fokkink, R. G.
- Polymer Chemistry, Vol. 10, Issue 23
Mapping the phase behavior of coacervate-driven self-assembly in diblock copolyelectrolytes
journal, January 2019
- Ong, Gary M. C.; Sing, Charles E.
- Soft Matter, Vol. 15, Issue 25
Micro- to macro-phase separation transition in sequence-defined coacervates
journal, January 2020
- Sing, Charles E.
- The Journal of Chemical Physics, Vol. 152, Issue 2
Polyelectrolyte Complexation of Oligonucleotides by Charged Hydrophobic—Neutral Hydrophilic Block Copolymers
journal, January 2019
- Marras, Alexander E.; Vieregg, Jeffrey R.; Ting, Jeffrey M.
- Polymers, Vol. 11, Issue 1
Langevin Dynamics Simulations of the Exchange of Complex Coacervate Core Micelles: The Role of Nonelectrostatic Attraction and Polyelectrolyte Length
journal, November 2019
- Bos, Inge; Sprakel, Joris
- Macromolecules, Vol. 52, Issue 22
Polyelectrolyte Complexation of Oligonucleotides by Charged Hydrophobic—Neutral Hydrophilic Block Copolymers
journal, January 2019
- Marras, Alexander E.; Vieregg, Jeffrey R.; Ting, Jeffrey M.
- Polymers, Vol. 11, Issue 1