Polyelectrolyte Solutions Research Articles

Constructing a Thin Layer of the Concentrated Polyelectrolyte Solution on the Hydrogel Surface That Can Considerably Improve the Solar Evaporation Efficiency

Constructing a Thin Layer of the Concentrated Polyelectrolyte Solution on the Hydrogel Surface That Can Considerably Improve the Solar Evaporation Efficiency

Competitive effects of anion mobility and viscous forces on the interactions of hyaluronic acid and alginic acid with hofmeister salts

The specific ion effect takes into account the hydration, mobility, and kosmotropic/chaotropic effects. However, another important aspect to consider is the solution viscosity, which influences ion mobility. A limited number of publications have considered the impact of specific ion effects on polyelectrolytes. However, none of the studies have considered the viscous effect of polyelectrolytes. This study aims to investigate the impact of kosmotropic and chaotropic anions on negatively charged alginic acid and hyaluronic acid using dynamic light scattering, rheology, and molecular dynamic simulations. Different concentration regimes and the change in the chain conformations in these regimes, along with the viscosity scaling and impact of the salts on the polyelectrolytes, have been discussed. An interesting finding regarding the solution viscosity was reported. The solution viscosity leads to the reversal of the diffusivity and viscosity trend of the polymer with kosmotropes and chaotropes. A threshold is also identified above which viscous forces dominate. Specific ion effects dominate below the threshold. It was concluded that the specific ion effect shows a competitive nature with the viscous forces in the case of a high-viscosity polyelectrolyte solution, which becomes an important aspect to consider for unveiling such interactions. Prior knowledge of the conformations of polymers can be used for designing drug delivery/nutrient delivery systems and for understanding phase separation behavior. Considering the viscosity of polymer solution becomes an important factor which, in turn, impacts the anion's mobility and ultimately influences the polymer conformations.

Harvesting Enhanced Blue Energy in Charged Nanochannels Using Semidiluted Polyelectrolyte Solution.

Blue energy generation in nanochannels based on salinity gradients is currently the most promising method in the area of nonconventional energy production. We used a semidiluted pure sodium carboxymethylcellulose (NaCMC)-KCl aqueous solution to study the characteristics of blue energy generation within a charged nanochannel. We solve the corresponding equations for ionic transport using a numerical technique based on the finite element method. Our analysis focused on the electric double layer (EDL) potential field, open circuit current, diffuse potential, electric conductance, maximum generated pore power, and maximum energy conversion efficiency by varying concentrations of the salt in the left-side reservoir and the bulk polyelectrolyte. The results indicate that as the polyelectrolyte concentration increases, the extent of EDL overlap considerably reduces. With an increase in polyelectrolyte concentration, the open circuit current increases, while the diffuse potential reduces. It was observed that both electrical conductance and maximal pore power improve considerably with higher polyelectrolyte concentrations. Interestingly, our modeling framework demonstrates a power density substantially higher (up to 16.31 W/m2) than earlier configurations and surpasses the established commercial limit (5 W/m2). Furthermore, our findings reveal that the reservoir salt concentration significantly affects the rate of decline in the maximum energy conversion efficiency as the polyelectrolyte concentration increases. The research paves the way for the development of high-power-density devices with several practical applications.

Diffusive Trends in Concentrated Oppositely-Charged Polyelectrolyte Solutions and Onset of Glassy Dynamics.

We utilize single particle tracking studies to investigate the diffusion of polylysine through concentrated matrices of cationic polylysine and anionic polyglutamic acid with no added salts. These studies show that diffusivity has a strong apparently exponential dependence on concentration in crowded systems that does not appear to be a function of the charge sign. These trends are consistent in both single-phase systems prepared at concentrated conditions and polymer-rich coacervate phases formed from dilute phase-separating systems. The likely origin of this behavior is the onset of glassy dynamics spurred by a decrease in plasticization by water and the large excluded volume associated with charge-bearing species. This effect can be contextualized through free volume-based theories such as the Vrentas-Duda model. Overall, we obtain dynamic behavior that is distinctly different from behavior observed in more dilute systems and warrants further investigation.

Oscillatory Interactions between Colloidal Particles in Polyelectrolyte Solutions: Linear Response Theory

Oscillatory Interactions between Colloidal Particles in Polyelectrolyte Solutions: Linear Response Theory

Two Methods Based on Integral Equation Approaches in Analyzing Polyelectrolyte Solutions: Macrophase Separation.

To understand the phase behaviors of polyelectrolyte solutions, we provide two analytical methods to formulate a molecular equation of state for a system of fully charged polyanions (PAs) and polycations (PCs) in a monomeric neutral component, based on integral equation theories. The mixture is treated in a primitive and restricted manner. The first method utilizes Blum's approach to charged hard spheres, incorporating the chain connectivity contribution by charged spheres via Stell's cavity function method. The second method employs Wertheim's multi-density Ornstein-Zernike treatment of charged hard spheres with Baxter's adhesive potential. The pressures derived from these methods are compared to available molecular dynamics simulations data for a solution of PAs and monomeric counterions as a limiting case. Two-phase equilibrium for the system is calculated using both methods to evaluate the relative strength of phase segregation that leads to complex coacervation. Additionally, the scaling exponents for a selected solution near its critical point are examined.

Critical adsorption and charge reversal in polyelectrolyte solutions: Analytical mean-field theory.

An analytical linearized mean-field theory is presented to describe the adsorption behavior of polyelectrolytes near charged colloidal surfaces with additional short-ranged non-electrostatic interactions. The coupling between the polyelectrolyte segment density and electrostatic potential is explicitly accounted for in a self-consistent manner. This coupling gives rise to highly non-linear behavior, such as oscillations of the electrostatic potential. We derive analytical expressions for the critical surface charge density σc, after which adsorption takes place, and recover the well-known σc∼ns3/2 scaling regime, where ns is the salt concentration. In addition, the theory yields a new ns1 scaling regime if the surface is hard and a unified ns1 scaling regime if the surface also possesses some short-ranged attraction with the polyelectrolyte. Furthermore, we derive an analytical expression to describe the critical polyelectrolyte concentration φc to achieve complete charge reversal, which is found to scale as φc ∼ σ2/(f2c2), where c is related to the magnitude of short-ranged interactions and f is the average charge per monomer of the polyelectrolyte. It is observed that within our theory, complete charge reversal can only take place if the short-ranged interactions are sufficiently strong to completely compensate for the entropy loss of adsorption.

GCMe: Efficient Implementation of the Gaussian Core Model with Smeared Electrostatic Interactions for Molecular Dynamics Simulations of Soft Matter Systems.

In recent years, molecular dynamics (MD) simulations have emerged as an essential tool for understanding the structure, dynamics, and phase behavior of charged soft matter systems. To explore phenomena across greater length and time scales in MD simulations, molecules are often coarse-grained for better computational performance. However, commonly used force fields represent particles as hard-core interaction centers with point charges, which often overemphasizes the packing effect and short-range electrostatics, especially in systems with bulky deformable organic molecules and systems with strong coarse-graining. This underscores the need for an efficient soft-core model to physically capture the effective interactions between coarse-grained particles. To this end, we implement a soft-core model uniting the Gaussian core model with smeared electrostatic interactions that is phenomenologically equivalent to recent theoretical models. We first parametrize it generically using water as the model solvent. Then, we benchmark its performance in the OpenMM toolkit for different boundary conditions to highlight a computational speedup of up to 34 × compared to commonly used force fields and existing implementations. Finally, we demonstrate its utility by investigating how boundary polarizability affects the adsorption behavior of a polyelectrolyte solution on perfectly conducting and nonmetal boundaries.

Why Single-Chain Nanoparticles from Weak Polyelectrolytes Can Be Synthesized at Large Scale in Concentrated Solution?

Here, the unresolved question of why single-chain nanoparticles (SCNPs) prepared from a weak polyelectrolyte (PE) precursor can be synthesized on a large is addresses, unlike SCNPs obtained from an equivalent neutral (nonamphiphilic) polymer precursor. The combination of the standard elastic single-chain nanoparticles (ESN) model -developed for neutral chains- with the classical scaling theory of PE solutions provides the key. Essentially, the long-range repulsion between electrostatic blobs in a weak PE precursor restricts the cross-linking process during SCNPs formation to the interior of each blob. Consequently, the maximum concentration at which PE-SCNPs can be prepared without interchain cross-linking is not determined by the full size of the PE precursor but, instead, by the smaller size of its electrostatic blobs. Therefore, PE-SCNPs can be synthesized up to a critical concentration where electrostatic blobs from different chains touch each other. This concentration can be 30 times higher than that for non-PE polymer precursors. Upon progressive dilution, the size of PE-SCNPs synthesized in concentrated solution increases until it reaches the bigger size of PE-SCNPs prepared under highly diluted conditions. PE-SCNPs do not adopt a globular conformation either in concentrated or in diluted solution. It shows that the main model predictions agree with experimental results.

Extreme dependence of dynamics on concentration in highly crowded polyelectrolyte solutions.

Charge-carrying species, such as polyelectrolytes, are vital to natural and synthetic processes that rely on their dynamic behavior. Through single-particle tracking techniques, the diffusivity of individual polyelectrolyte chains and overall system viscosity are determined for concentrated polylysine solutions. These studies show scaling dependences of D ~ c-6.1 and η ~ c7.2, much stronger than theoretical predictions, drawing the applicability of power law fits into question. Similar trends are observed in concentrated solutions prepared at various pH and counterion conditions. These hindered system dynamics appear universal to polyelectrolyte systems and are attributed to the large effective excluded volumes of polyelectrolyte chains inducing glassy dynamics. The framework of the Vrentas-Duda free-volume theory is used to compare polyelectrolyte and neutral systems. Supported by this theory, excluding counterion mass from total polymer mass results in all environmental conditions collapsing onto a common trendline. These results are applicable to crowded biological systems, such as intracellular environments where protein mobility is strongly inhibited.

Bubbling up in a Lab-on-a-Chip: A gravity-driven approach to the formation of polyelectrolyte multilayer capsules and foams

The generation of multi-functional capsules often requires the sequential deposition of different components on the surface of bubbles or drops. Batch-based methods lack fine control over the capsule sizes, including risk of fusion, and cannot ensure identical environments for each capsule. To overcome these issues, different micro/milli-fluidic methods have been developed in the past. However, a major challenge remains in combining an explicit and flexible control over the capsule generation and their residence time in the different solutions within the same device. Using for the first time the example of bubbles covered by layers of oppositely charged polyelectrolytes (PSS/PAH), we introduce an original millifluidic Lab-on-a-Chip device with two novel functions: (1) Size and separation of the bubbles are tuned at constant flow conditions via gas injection through a movible, circular dispense tip into the cross-flow of a rectangular channel. We provide a detailed exploration of the bubbling parameters together with physical justification of the observations. (2) The device exploits gravity to make the generated bubbles rise between horizontally stacked millifluidic chips containing each the controlled flow of a specific polyelectrolyte solution. In analogy with electric circuits, we show how the flow resistance of each chip can be adapted such that bubbles move smoothly between them while avoiding undesired mixing of the solutions. We show first examples of obtained multilayer capsules and discuss their peculiar features, in particular, their outstanding stability with respect to coalescence and dissolution. While our methods use polyelectrolyte assembly on bubbles, they can be readily transferred to other types of solutions or even to drops and particles.

Microstructures and Rheological Properties of Short-Side-Chain Perfluorosulfonic Acid in Water/2-Propanol.

The viscosity and viscoelasticity of polyelectrolyte solutions with a single electrostatic interaction have been carefully studied experimentally and theoretically. Despite some theoretical models describe experimental results well, the influence of multiple interactions (electrostatic and hydrophobic) on rheological scaling is not yet fully resolved. Herein, we systematically study the microstructures and rheological properties of short-side-chain perfluorosulfonic acid (S-PFSA), the most promising candidate of a proton exchange membrane composed of a hydrophobic backbone with hydrophilic side-chains, in water/2-propanol. Small-angle X-ray scattering confirms that semiflexible S-PFSA colloidal particles with a length of ~38 nm and a diameter of 1-1.3 nm are formed, and the concentration dependence of the correlation length (ξ) obeys the power law ξ~c-0.5 consistent with the prediction of Dobrynin et al. By combining macrorheology with diffusing wave spectroscopy microrheology, the semidilute unentangled, semidilute entangled, and concentrated regimes corresponding to the scaling relationships ηsp~c0.5, ηsp~c1.5, and ηsp~c4.1 are determined. The linear viscoelasticity indicates that the entanglement concentration (ce) obtained from the dependence of ηsp on the polymer concentration is underestimated owing to hydrophobic interaction. The true entanglement concentration (cte) is obtained by extrapolating the plateau modulus (Ge) to the terminal modulus (Gt). Furthermore, Ge and the plateau width, τr/τe (τr and τe denote reptation time and Rouse time), scale as Ge~c2.4 and τr/τe~c4.2, suggesting that S-PFSA dispersions behave like neutral polymer solutions in the concentrated regime. This work provides mechanistic insight into the rheological behavior of an S-PFSA dispersion, enabling quantitative control over the flow properties in the process of solution coating.

Exploring temperature effects on raw polysaccharide in semi-diluted solution using complex conductivity: Correlation analysis of activation energies

The evolution of the complex conductivity of raw polysaccharides extracted from Cystoseira myriophyloides algae exhibited significant temperature dependence in an aqueous solution. An analysis of the complex conductivity versus frequency was conducted using an appropriate electrical circuit based on our theoretical approach. This facilitated the generation of analytical functions representing the relaxation processes occurring at different temperatures. Subsequently, extrapolation and deconvolution procedures were employed to further investigate and identify all relaxation processes and their origins. These approaches revealed the presence of three relaxation processes. The first relaxation, observed at low frequency, is attributed to interfacial polarization between the electrode and the solution. The second and third relaxations, observed at medium and high frequencies, are attributed to bulk relaxation processes. Then, subtracting the low-frequency process clarified the bulk relaxation processes. Both relaxations are described by the Cole-Cole relaxation, which effectively models the well-known Maxwell-Wagner-Sillars (MWS) phenomenon typically observed in polyelectrolyte solutions. This relaxation is typically caused by interfacial polarization between molecular chains and counterions in the sample. Both relaxations were found to be thermally activated. The temperature dependence of useful parameters extracted from each relaxation, such as relaxation time (τσ) and conductivity (σdc) and (σ∞), followed Arrhenius law behavior. Furthermore, activation energy values for each relaxation process were determined, establishing a linear correlation between activation energy values related to relaxation time (τσ) and both conductivities (σdc) and (σ∞). These results confirm the origin of bulk relaxations and demonstrate a strong link between relaxation and conduction mechanisms.

Underwater Fabrication of Carbon Nanotube/Coacervate Composites.

Soft conductive materials are of interest for a wide range of applications, but their syntheses have remained difficult. Herein, we present a convenient route for underwater fabrication of a composite made of carbon nanotubes (CNTs) and mussel-inspired complex coacervates. The key to success of this method is that CNTs were solubilized very effectively in protocoacervates, which are high-concentration solutions of polyelectrolytes at a pH where only one of them is charged, thereby impeding coacervate formation. Composite materials were formed by the simple injection of CNT-dispersed protocoacervate solutions into water under ambient conditions. The method is simple, fast, and ecofriendly, and composites of CNT-complex coacervate in the form of films or bulk materials were obtained. The composites demonstrated electrical conductivity and tunable mechanical properties, which depended on the concentration of polyelectrolytes and the CNT:protocoacervate ratio. Hence, the composites can be manipulated to attain diverse properties, for examples, tunable reduced modulus (15 to 32 GPa) and hardness (0.3 to 0.7 GPa) as well as an electrical conductivity of up to 4 × 103 S m-1.

A microfluidic platform for automatic continuous flow layer‐by‐layer assembly of polymer multilayered nanofilms

AbstractCapillary flow layer‐by‐layer assembly is a microfluidic platform for high throughput preparation and screening of multilayered polymer nanofilms. However, it is time‐consuming and labor‐intensive, since the switching of polyelectrolyte solutions is done manually. As the emergence of flow chemistry and microdevices for artificial intelligence‐based lab automation, an automatic system that can switch polymer solutions and washing liquids is urgently needed for building functional LbL films inside microfluidic devices. Herein, we construct a continuous flow (ConF)‐layer‐by‐layer (LbL) device that can automatically fabricate polymer nanofilms inside a microfluidic device. By including a flow separator and a mixer (a model polyelectrolyte pair), chitosan and carboxymethyl cellulose can be deposited inside a microfluidic device using the ConF‐LbL system. Resulting nanofilms are studied by investigating thickness and surface roughness of the nanofilms and comparing with the other conventional LbL methods. The acid dissolution method was used to compare the differences in stability between nanofilms made from ConF‐LbL and static immersive method in similar conditions. Furthermore, by using one optimized film formulation for coating on the inside walls of a microfluidic chip, we successfully demonstrated the ability of this device to capture cancer cells in whole blood. This ConF‐LbL platform is expected to be a convenient tool to coat functional nanofilms inside microdevices for biomedical and sensor applications.

Structure and properties of electrochemical interfaces with grafting polyelectrolyte: A fluid density functional theory study

The structure of the electrode/electrolyte interface directly determines electrochemical performance. One effective method for controlling this interface structure is by grafting polyelectrolyte onto the electrode surface, which can significantly alter the double layer structure and enhance electrochemical performance. This study focuses on the graft modification of polyelectrolytes at the electrochemical interface and investigates the impact of the length and density of the grafted polyelectrolyte chain on the structure and capacitance of the electrode/ionic liquid interface using fluid density functional theory (FDFT). The findings indicate that the grafted polymerbrush disrupts the alternating layer of anions and cations at the conventional interface and exerts an additional adsorption effect on counter ions, thereby reducing the density of freely movable co-ions. Consequently, this process increases the effective charge and capacitance of the interface. The results of this investigation contribute to a deeper comprehension of polyelectrolyte solutions at solid–liquid interfaces and guide the regulation of electrochemical interface properties.

Charge Regulation Effects in Polyelectrolyte Adsorption.

Polyelectrolyte (PE) adsorption plays a pivotal role in tailoring surface properties, finding diverse applications across scientific and industrial domains. In aqueous environments, these polymers gain charge through the dissociation equilibrium of ionizable groups. Consequently, accurately representing their electrostatic interactions necessitates considering many-body couplings between charge and configuration-a phenomenon known as charge regulation (CR)-instead of relying on the constant charge approximation. Here, we show that CR effects can significantly enhance PE adsorption. In the vicinity of a like-charged interface, where short-range PE-surface attraction drives adsorption, both PEs and the surface undergo a reduction in charges during the adsorption process, especially in a semidilute PE solution. This reduction in charges leads to a noticeable decrease in the electrostatic repulsion barrier, facilitating the adsorption process. Conversely, near an oppositely charged surface, CR effects enhance the electrostatic charges of both PEs and surfaces coherently, suppressing the charge reversal of surface charges and ultimately promoting adsorption. These findings underscore the crucial CR effects in PE adsorption and challenge the direct use of electrostatic charges, typically estimated in bulk systems, for an accurate understanding of adsorption phenomena.

Origin of Anomalously Large Depletion Zones in Like-Charged Colloid-Polyelectrolyte Mixtures.

Depletion zones in polyelectrolyte solutions in contact with like-charged flat surfaces are investigated. Using a coupled self-consistent field and Debye-Hückel approach, an explicit expression for the thickness δ of the depletion layer is derived. It is found that δ∼δ_{n}+cκ^{-1}, where δ_{n} is the depletion thickness at a neutral surface, c is a function of the electrostatic characteristics of the system, and κ^{-1} is the Debye length. It is argued that the theory still holds beyond the mean-field approximation, which is confirmed by quantitative agreement between our theoretical results and experiments.

Effect of ion distribution on stress relaxation in polyelectrolyte complex gels.

Solutions of polyelectrolytes consisting of polycations and polyanions in equal proportions were studied in the present work. Due to the physical cross-links formed by the charged groups, physical gels were formed in such systems. The mechanical properties and structure of the obtained gels depending on the charge arrangement along the backbone and the dimensionless Bjerrum length λ were investigated. The response of the systems to a uniaxial affine deformation was studied first. It was found that the systems can be divided into three groups depending on the charge arrangement: showing an almost elastic response; showing a viscoelastic response with a very long relaxation time; and showing a weak viscoelastic response with a short relaxation time. Interestingly, no stable aggregates were formed in the systems with the charges located on spacers, probably because of the increased mobility of the charges in such systems. The obtained stress relaxation curves had different functional forms, indicating that the relaxation has at least two characteristic times, which are different for different systems. In order to understand the molecular nature of the observed mechanical response, the temporal evolution of the network structure of a system showing a viscoelastic response with a very long relaxation time was studied; the aggregates were found to be dynamic, which leads to the relaxation of the "subchains" conformation.

Dilute polyelectrolyte solutions: recent progress and open questions.

Polyelectrolytes are a class of polymers possessing ionic groups on their repeating units. Since counterions can dissociate from the polymer backbone, polyelectrolyte chains are strongly influenced by electrostatic interactions. As a result, the physical properties of polyelectrolyte solutions are significantly different from those of electrically neutral polymers. The aim of this article is to highlight key results and some outstanding questions in the polyelectrolyte research from recent literature. We focus on the influence of electrostatics on conformational and hydrodynamic properties of polyelectrolyte chains. A compilation of experimental results from the literature reveals significant disparities with theoretical predictions. We also discuss a new class of polyelectrolytes called poly(ionic liquid)s that exhibit unique physical properties in comparison to ordinary polyelectrolytes. We conclude this review by listing some key research challenges in order to fully understand the conformation and dynamics of polyelectrolytes in solutions.