The Polyelectrolyte Complex/Coacervate Continuum

Wang, Qifeng; Schlenoff, Joseph B.

doi:10.1021/ma500500q

Cited by 473 publications

(797 citation statements)

References 50 publications

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“…Rheological characterization demonstrated that these trends correlate with decreasing coacervate viscosity with increasing salt concentration ( Figure 5a) [71,79,157]. Furthermore, the viscosity was seen to increase as a function of degree of polymerization ( Figure 5b) [79], as would be expected for polymeric materials.…”

Section: Viscositymentioning

confidence: 55%

Linear viscoelasticity of complex coacervates

Liu

Winter

Perry

2017

Advances in Colloid and Interface Science

128

163

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Rheology is a powerful method for materials characterization that can provide detailed information about the self-assembly, structure, and intermolecular interactions present in a material. Here, we review the use of linear viscoelastic measurements for the rheological characterization of complex coacervate-based materials. Complex coacervation is an electrostatically and entropically-driven associative liquid-liquid phase separation phenomenon that can result in the formation of bulk liquid phases, or the self-assembly of hierarchical, microphase separated materials. We discuss the need to link thermodynamic studies of coacervation phase behavior with characterization of material dynamics, and provide parallel examples of how parameters such as charge stoichiometry, ionic strength, and polymer chain length impact self-assembly and material dynamics. We conclude by highlighting key areas of need in the field, and specifically call for the development of a mechanistic understanding of how molecular-level interactions in complex coacervate-based materials affect both selfassembly and material dynamics.

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Section: Viscositymentioning

confidence: 55%

Linear viscoelasticity of complex coacervates

Liu

Winter

Perry

2017

Advances in Colloid and Interface Science

128

163

View full text Add to dashboard Cite

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“…147 The entropic forces also arise from reorganization of water molecules around the polymer chains during the complexation process as evidenced in recent experiments. 55 …”

Section: Electrostatically Driven Structure In Polyelectrolyte Solutionsmentioning

confidence: 99%

50th Anniversary Perspective: A Perspective on Polyelectrolyte Solutions

2017

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From the beginning of life with the information-containing polymers until the present era of a plethora of water-based materials in health care industry and biotechnology, polyelectrolytes are ubiquitous with a broad range of structural and functional properties. The main attribute of polyelectrolyte solutions is that all molecules are strongly correlated both topologically and electrostatically in their neutralizing background of charged ions in highly polarizable solvent. These strong correlations and the necessary use of numerous variables in experiments on polyelectrolytes have presented immense challenges toward fundamental understanding of the various behaviors of charged polymeric systems. This Perspective presents the author’s subjective summary of several conceptual advances and the remaining persistent challenges in the contexts of charge and size of polymers, structures in homogeneous solutions, thermodynamic instability and phase transitions, structural evolution with oppositely charged polymers, dynamics in polyelectrolyte solutions, kinetics of phase separation, mobility of charged macromolecules between compartments, and implications to biological systems.

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“…Furthermore, the nature of the charged species must allow for the formation of a 'coacervate', which represents a subset of complexes that undergo a liquid-liquid phase separation rather than forming solid precipitates. [1][2][3][4][5][6] Historical and current investigations into complex coacervates have studied the formation of such phases in natural polymers, such as proteins or polysaccharides, which are currently widely used as food additives. [7][8][9][10][11][12][13][14][15][16][17][18] Despite the utility of these systems, there has only recently been a resurgence of interest in their molecular behavior, in particular for its promise as a powerful route to self-assembled materials such as micelles, 3,[19][20][21][22] block copolymers, [23][24][25][26] and layer-bylayer assembly.…”

Section: Introductionmentioning

confidence: 99%

PRISM-Based Theory of Complex Coacervation: Excluded Volume versus Chain Correlation

2015

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Aqueous solutions of oppositely-charged polyelectrolytes can undergo liquid-liquid phase separation into materials known as complex coacervates. These coacervates have been a subject of intense experimental and theoretical interest. Efforts to provide a physical description of complex coacervates have led to a number of theories that qualitatively (and sometimes quantitatively) agree with experimental data. However, this agreement often occurs in a degeneracy of models with profoundly different starting assumptions and different levels of sophistication. Theoretical difficulties in these systems are similar to those in most polyelectrolyte systems where charged species are highly correlated. These highly-correlated systems can be described using Liquid State (LS) integral equation theories, which surpass mean field theories by providing information * To whom correspondence should be addressed † University of Massachusetts Amherst ‡ University of Illinois Urbana-Champaign 1 on local charge ordering. We extend these ideas to complex coacervate systems using PRISM-type theories, and are able to capture effects not observable in traditional coacervate models, particularly connectivity and excluded volume effects. We can thus bridge two traditional but incommensurate theories meant to describe complex coacervates: the Voorn-Overbeek theory and counterion release. Importantly, we hypothesize that a cancellation of connectivity and excluded volume effects provides an explanation for the ability of Voorn-Overbeek theory to fit experimental data despite its well-known approximations.

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The Polyelectrolyte Complex/Coacervate Continuum

Cited by 473 publications

References 50 publications

Linear viscoelasticity of complex coacervates

Linear viscoelasticity of complex coacervates

50th Anniversary Perspective: A Perspective on Polyelectrolyte Solutions

PRISM-Based Theory of Complex Coacervation: Excluded Volume versus Chain Correlation

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