Binodal Compositions of Polyelectrolyte Complexes

Spruijt, Evan; Westphal, Adrie H.; Borst, Jan Willem; Stuart, Martien A. Cohen; Gucht, Jasper van der

doi:10.1021/ma101031t

Cited by 387 publications

(789 citation statements)

References 37 publications

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“…"# --value is also in good agreement with the stoichiometry found in ITC on the same compounds. We have found that stoichiometric PSS/PDADMAC mixtures without added salt form a viscous coacervate phase that sedimented rapidly [63,64]. Observed between glass slides, the coacervate appears as 5 µm droplets (Fig.…”

Section: Iii1 - Assessment Of the Pacts Technique Using Ion--containmentioning

confidence: 85%

Polyelectrolyte assisted charge titration spectrometry: Applications to latex and oxide nanoparticles

Mousseau

Vitorazi

Herrmann

et al. 2016

Journal of Colloid and Interface Science

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Abstract:The electrostatic charge density of particles is of paramount importance for the control of the dispersion stability. Conventional methods use potentiometric, conductometric or turbidity titration but require large amount of samples. Here we report a simple and cost--effective method called polyelectrolyte assisted charge titration spectrometry or PACTS. The technique takes advantage of the propensity of oppositely charged polymers and particles to assemble upon mixing, leading to aggregation or phase separation. The mixed dispersions exhibit a maximum in light scattering as a function of the volumetric ratio , and the peak position !"# is linked to the particle charge density according to ~ ! !"# where ! is the particle diameter. The PACTS is successfully applied to organic latex, aluminum and silicon oxide particles of positive or negative charge using poly(diallyldimethylammonium chloride) and poly(sodium 4--styrenesulfonate). The protocol is also optimized with respect to important parameters such as pH and concentration, and to the polyelectrolyte molecular weight. The advantages of the PACTS technique are that it requires minute amounts of sample and that it is suitable to a broad variety of charged nano--objects.

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Section: Iii1 - Assessment Of the Pacts Technique Using Ion--containmentioning

confidence: 85%

Polyelectrolyte assisted charge titration spectrometry: Applications to latex and oxide nanoparticles

Mousseau

Vitorazi

Herrmann

et al. 2016

Journal of Colloid and Interface Science

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“…An example of these types of detailed binodal curves is shown in Figure 3 for the system of poly(acrylic acid) (PAA) in complex with poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), in the presence of KCl [78]. The phase behavior of this system was analyzed only for a 1:1 stoichiometric (charge-neutral) mixture of PAA and PDMAEMA, rather than for the entire range of PAA-PDMAEMA-KCl composition space depicted in Figure 3b.…”

Section: Connecting Coacervate Phase Behavior With Materials Dynamicsmentioning

confidence: 99%

Linear viscoelasticity of complex coacervates

Liu

Winter

Perry

2017

Advances in Colloid and Interface Science

129

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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“…Despite these recent advances, VO theory continues to be used to explain experimental data because of its inherent simplicity and applicability for a wide range of systems. Recently, for example, Spruijt et al [10] adapted the VO theory to describe complexation behavior of charge-stoichiometric compositions of synthetic polyelectrolytes, poly(acrylic acid) (PAA) and poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), and obtained good agreement with experiments. Priftis et al [34] have also used a modified version of the VO theory to explain complexation behavior in ternary systems composed of a polycation with two polyanions: (1) PAA with PDMAEMA and poly(allylamine) (PAH), and (2) PAA with PDMAEMA and poly(ethylenimine) (PEI).…”

Section: Introductionmentioning

confidence: 98%

“…Oparin's hypothesis has however been dismissed in modern theories of the origin of life, particularly after the discovery of DNA as the genetic material [7]. Most of the earlier studies on polyelectrolyte complexation focused on coacervation of natural polymers such as albumin and gelatin, but recent studies [2,3,[8][9][10][11][12] have extended this to the complexation of synthetic polyelectrolytes. Renewed scientific interest in polyelectrolyte complexation is due, in part, to its use in polyelectrolyte assemblies and multilayer films [13,14], which have many technological applications [15,16].…”

Section: Introductionmentioning

confidence: 99%

“…In particular, we focus on the effects of pH variations that result in changes in the degree of dissociation of polyions. We test the performance of the theory with experimental data borrowed from published literature [1,10,35] and our own experiments on systems containing PAA as the polyacid, and PDMAEMA or poly(diallyldimethyl ammonium chloride) (PDADMAC) as the polybase. For electrostatically-driven complexation, we expect that the critical salt concentration for phase separation (phase separation regime) is maximum for intermediate pH (∼ 6.5) conditions, when both PAA and PDMAEMA are highly charged.…”

Section: Introductionmentioning

confidence: 99%

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pH and Salt Effects on the Associative Phase Separation of Oppositely Charged Polyelectrolytes

et al. 2014

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Abstract:The classical Voorn-Overbeek thermodynamic theory of complexation and phase separation of oppositely charged polyelectrolytes is generalized to account for the charge accessibility and hydrophobicity of polyions, size of salt ions, and pH variations. Theoretical predictions of the effects of pH and salt concentration are compared with published experimental data and experiments we performed, on systems containing poly(acrylic acid) (PAA) as the polyacid and poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) or poly(diallyldimethyl ammonium chloride) (PDADMAC) as the polybase. In general, the critical salt concentration below which the mixture phase separates, increases with degree of ionization and with the hydrophobicity of polyelectrolytes. We find experimentally that as the pH is decreased below 7, and PAA monomers are neutralized, the critical salt concentration increases, while the reverse occurs when pH is raised above 7. We predict this asymmetry theoretically by introducing a large positive Flory parameter (= 0.75) for the interaction of neutral PAA monomers with water. This large positive Flory parameter is supported by molecular dynamics simulations, which show much weaker hydrogen bonding between neutral PAA and water than between charged PAA and water, while neutral and charged PDMAEMA show similar numbers of hydrogen bonds. This increased hydrophobicity of neutral PAA at reduced pH increases the tendency towards phase separation despite the reduction in charge interactions between the polyelectrolytes. Water content and volume of coacervate are found to be a strong function of the pH and salt concentration.

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Binodal Compositions of Polyelectrolyte Complexes

Cited by 387 publications

References 37 publications

Polyelectrolyte assisted charge titration spectrometry: Applications to latex and oxide nanoparticles

Polyelectrolyte assisted charge titration spectrometry: Applications to latex and oxide nanoparticles

Linear viscoelasticity of complex coacervates

pH and Salt Effects on the Associative Phase Separation of Oppositely Charged Polyelectrolytes

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