Relaxation Behavior by Time-Salt and Time-Temperature Superpositions of Polyelectrolyte Complexes from Coacervate to Precipitate

Complexation between anionic and cationic polyelectrolytes results in solid-like precipitates or liquid-like coacervate depending on the added salt in the aqueous medium. However, the boundary between these polymer-rich phases is quite broad and the associated changes in the polymer relaxation in the complexes across the transition regime are poorly understood. In this work, the relaxation dynamics of complexes across this transition is probed over a wide timescale by measuring viscoelastic spectra and zero-shear viscosities at varying temperatures and salt concentrations for two different salt types. We find that the complexes exhibit time-temperature superposition (TTS) at all salt concentrations, while the range of overlapped-frequencies for time-temperature-salt superposition (TTSS) strongly depends on the salt concentration (Cs) and gradually shifts to higher frequencies as Cs is decreased. The sticky-Rouse model describes the relaxation behavior at all Cs. However, collective relaxation of polyelectrolyte complexes gradually approaches a rubbery regime and eventually exhibits a gel-like response as Cs is decreased and limits the validity of TTSS.Comment: 12 pages, 5 figures, Follow Gels journal link for latest versio

Like-charge polymer-membrane complexation mediated by multivalent cations: one-loop-dressed strong coupling theory

We probe the electrostatic mechanism driving adsorption of polyelectrolytes onto like-charged membranes upon the addition of tri- and tetravalent counterions to a bathing monovalent salt solution. We develop a one-loop-dressed strong coupling theory that treats the monovalent salt at the electrostatic one-loop level and the multivalent counterions within a strong-coupling approach. It is shown that the adhesive force of the multivalent counterions mediating the like-charge adsorption arises from their strong condensation at the charged membrane. The resulting interfacial counterion excess locally maximizes the screening ability of the electrolyte and minimizes the electrostatic polymer grand potential. This translates into an attractive force that pulls the polymer to the similarly charged membrane. We show that the high counterion valency enables this adsorption transition even at weakly charged membranes. Additionally, strongly charged membranes give rise to salt-induced correlations and intensify the interfacial multivalent counterion condensation, strenghtening the complexation of the polymer with the like-charged membrane, as well as triggering the orientational transition of the molecule prior to its adsorption. Finally, our theory provides two additional key features as evidenced by previous adsorption experiments: first, the critical counterion concentration for polymer adsorption decreases with the rise of the counterion valency, and second, the addition of monovalent salt enhances the screening of the membrane charges and suppresses salt correlations. This weakens the interfacial multivalent counterion condensation and results in the desorption of the polymer from the substrate

One-Step Generation of Multifunctional Polyelectrolyte Microcapsules via Nanoscale Interfacial Complexation in Emulsion (NICE)

Polyelectrolyte microcapsules represent versatile stimuli-responsive structures that enable the encapsulation, protection, and release of active agents. Their conventional preparation methods, however, tend to be time-consuming, yield low encapsulation efficiency, and seldom allow for the dual incorporation of hydrophilic and hydrophobic materials, limiting their widespread utilization. In this work, we present a method to fabricate stimuli-responsive polyelectrolyte microcapsules in one step based on nanoscale interfacial complexation in emulsions (NICE) followed by spontaneous droplet hatching. NICE microcapsules can incorporate both hydrophilic and hydrophobic materials and also can be induced to trigger the release of encapsulated materials by changes in the solution pH or ionic strength. We also show that NICE microcapsules can be functionalized with nanomaterials to exhibit useful functionality, such as response to a magnetic field and disassembly in response to light. NICE represents a potentially transformative method to prepare multifunctional nanoengineered polyelectrolyte microcapsules for various applications such as drug delivery and cell mimicry.112823Ysciescopu

Complexation and coacervation of like-charged polyelectrolytes inspired by mussels

It is well known that polyelectrolyte complexes and coacervates can form on mixing oppositely charged polyelectrolytes in aqueous solutions, due to mainly electrostatic attraction between the oppositely charged polymers. Here, we report the first (to the best of our knowledge) complexation and coacervation of two positively charged polyelectrolytes, which provides a new paradigm for engineering strong, self-healing interactions between polyelectrolytes underwater and a new marine mussel-inspired underwater adhesion mechanism. Unlike the conventional complex coacervate, the like-charged coacervate is aggregated by strong short-range cation-p interactions by overcoming repulsive electrostatic interactions. The resultant phase of the like-charged coacervate comprises a thin and fragile polyelectrolyte framework and round and regular pores, implying a strong electrostatic correlation among the polyelectrolyte frameworks. The like-charged coacervate possesses a very low interfacial tension, which enables this highly positively charged coacervate to be applied to capture, carry, or encapsulate anionic biomolecules and particles with a broad range of applications.113320Ysciescopu

The parallel lives of polysaccharides in food and pharmaceutical formulations

The present opinion article discusses how polysaccharide structures can be used in both food and pharmaceutical formulations. We distinguish two regions depending on moisture content where polysaccharides form structures with distinct functional properties. Some trends in key areas of active research are assessed and in particular edible films, encapsulation, polycrystalline polysaccharides, protein-polysaccharide coacervation and fluid gels. We unveil that the physicochemical principles that are shared across the food and pharmaceutical disciplines provide a great opportunity for cross-disciplinary collaboration. We finally argue that such co-operation will help tackling polysaccharide functionality issues that are encountered in both areas

Sphere-to-cylinder transition in hierarchical electrostatic complexes

We report the formation of colloidal complexes resulting from the electrostatic co-assembly between anionic surfactants and cationic polyelectrolytes or block copolymers. Combining light and x-ray scattering experiments with cryogenic transmission and optical microscopy, we emphasize a feature rarely addressed in the formation of the electrostatic complexes, namely the role of the mixing concentration on the microstructure. At low mixing concentration, electrostatic complexes made from cationic-neutral copolymers and alkyl sulfate surfactants exhibit spherical core-shell microstructures. With increasing concentration, the complexes undergo a sphere-to-cylinder transition, yielding elongated aggregates with diameter 50 nm and length up to several hundreds of nanometers. From the comparison between homo- and diblock polymer phase behaviors, it is suggested that the unidimensional growth is driven by the ability of the surfactant to self-assemble into cylindrical micelles, and in particular when these surfactants are complexed with oppositely charged polymers.Comment: 7 pages, 9 figures, 2 tables paper accepted at Colloid and Polymer Science, 31-Mar-0

Overcharging and reentrant condensation of thermoresponsive ionic microgels

We investigated the complexation of thermoresponsive anionic poly(N-isopropylacrylamide) (PNiPAM) microgels and cationic $\epsilon$-polylysine ($\epsilon$-PLL) chains. By combining electrophoresis, light scattering, transmission electron microscopy (TEM) and dielectric spectroscopy (DS) we studied the adsorption of $\epsilon$-PLL onto the microgel networks and its effect on the stability of the suspensions. We show that the volume phase transition (VPT) of the microgels triggers a large polyion adsorption. Two interesting phenomena with unique features occur: a temperature-dependent microgel overcharging and a complex reentrant condensation. The latter may occur at fixed polyion concentration, when temperature is raised above the VPT of microgels, or by increasing the number density of polycations at fixed temperature. TEM and DS measurements unambiguously show that short PLL chains adsorb onto microgels and act as electrostatic glue above the VPT. By performing thermal cycles, we further show that polyion-induced clustering is a quasi-reversible process: within the time of our experiments large clusters form above the VPT and partially re-dissolve as the mixtures are cooled down. Finally we give a proof that the observed phenomenology is purely electrostatic in nature: an increase of the ionic strength gives rise to the polyion desorption from the microgel outer shell.Comment: 15 Figure

Effect of surfactant concentration on the responsiveness of a thermoresponsive copolymer/surfactant mixture with potential application on Smart foams formulations

We studied a system formed by a mixture of a thermoresponsive negatively charged graft copolymer (Alg-g-PNIPAAm) with a brush-type structure, and an oppositely charged surfactant (DTAB), in bulk and at the air-solution interface. We performed experiments of surface tension, electrophoretic mobility, dynamic and static light scattering and atomic force microscopy in order to characterize the complexes formed as a function of DTAB concentration and temperature. We found that these polymer-surfactant complexes are able to respond by changing their sizes, both in bulk and at the air-solution interface, when T is increased above the coil-globule transition temperature (LSCT) of the copolymer. However, the thermoresponse was found to be dependent on surfactant concentration, cs: for cs < 2.8 mM, the size of the aggregates decreases as T increases but, for cs >= 2.8 mM, the opposite behavior takes place, i.e. the size increases with T. At the interface, the intensity of the effect produced on the surface tension by increasing T above LCST diminishes continuously as cs increases, reducing the ability of the interfacial complex to respond to temperature changes. We studied the stability of aqueous foams formulated with these mixtures as a function of T and cs. We found that the stability of the foam can be modulated by changing T, but we observed that this effect is dependent on the surfactant concentration range. We found a correlation between changes in the aggregates sizes, the surface tension behavior and the responsiveness of foam stability to changes of temperature

Induced Crystallization of Polyelectrolyte-Surfactant Complexes at the Gas-Water Interface

Synchrotron-X-ray and surface tension studies of a strong polyelectrolyte (PE) in the semi-dilute regime (~ 0.1M monomer-charges) with varying surfactant concentrations show that minute surfactant concentrations induce the formation of a PE-surfactant complex at the gas/solution interface. X-ray reflectivity and grazing angle X-ray diffraction (GIXD) provide detailed information of the top most layer, where it is found that the surfactant forms a two-dimensional liquid-like monolayer, with a noticeable disruption of the structure of water at the interface. With the addition of salt (NaCl) columnar-crystals with distorted-hexagonal symmetry are formed.Comment: 4 pages, 5 eps figure