Polyelectrolyte Adsorption Research Articles

Adsorption of polyelectrolytes in the presence of varying dielectric discontinuity between solution and substrate.

We examine the interactions between polyelectrolytes (PEs) and uncharged substrates under conditions corresponding to a dielectric discontinuity between the aqueous solution and the substrate. To this end, we vary the relevant system characteristics, in particular the substrate dielectric constant ɛs under different salt conditions. We employ coarse-grained molecular dynamics simulations with rodlike PEs in salt solutions with explicit ions and implicit water solvent with dielectric constant ɛw = 80. As expected, at low salt concentrations, PEs are repelled from the substrates with ɛs < ɛw but are attracted to substrates with a high dielectric constant due to image charges. This attraction considerably weakens for high salt and multivalent counterions due to enhanced screening. Furthermore, for monovalent salt, screening enhances adsorption for weakly charged PEs, but weakens it for strongly charged ones. Meanwhile, multivalent counterions have little effect on weakly charged PEs, but prevent adsorption of highly charged PEs, even at low salt concentrations. We also find that correlation-induced charge inversion of a PE is enhanced close to the low dielectric constant substrates, but suppressed when the dielectric constant is high. To explore the possibility of a PE monolayer formation, we examine the interaction of a pair of like-charged PEs aligned parallel to a high dielectric constant substrate with ɛs = 8000. Our main conclusion is that monolayer formation is possible only for weakly charged PEs at high salt concentrations of both monovalent and multivalent counterions. Finally, we also consider the energetics of a PE approaching the substrate perpendicular to it, in analogy to polymer translocation. Our results highlight the complex interplay between electrostatic and steric interactions and contribute to a deeper understanding of PE-substrate interactions and adsorption at substrate interfaces with varying dielectric discontinuities from solution, ubiquitous in biointerfaces, PE coating applications, and designing adsorption setups.

On the determination of charge and nitrogen content in cellulose fibres modified to contain quaternary amine functionality

Research interest in quaternization of cellulose fibres has increased considerably over the past decades. However, there is little or no consensus regarding how to characterize the material in terms of degree of substitution (DS), and the literature suggests a range of different methods focusing on charge determination as well as nitrogen content quantification. This work aims to fill the knowledge gap regarding how the different methods perform in relation to each other, and for what cellulosic systems each method has advantages, disadvantages and even potential pitfalls. FT-IR and NMR measurements are used to establish successful modification and determine the relative number of substituent groups. Another six methods are compared for the determination of the DS of cellulosic fibres and nanofibrils. The methods include Kjeldahl measurements, nitrogen determination by chemiluminescence, determination of molecular nitrogen by the Dumas method, colloidal titration, conductometric titration and polyelectrolyte adsorption. It can be concluded that most techniques investigated are reliable within certain ranges of DS and/or when using appropriate post-treatment of the quaternized material and suitable sample preparation techniques. The results from the present work hence provide recommendations to make an educated choice of method, and experimental protocol, based on the technique at hand.

3D- printed modular spr platform integrated with ellipsometer for in-situ label-free optical sensing applications

The present work focuses on advancing optical sensing abilities through the instrumentation of Surface Plasmon Resonance Spectroscopy (SPR) with a commercial ellipsometer. This approach involves the incorporation of an in-house-built 3D-printed SPR module to circumvent the complexity of optical alignments with the ellipsometer. Currently, no commercially available SPR-enhanced Ellipsometry (SPRE) system exists, and previous systems are mostly custom-designed. Our work addresses this gap by introducing an in-house-built SPR module compatible with Ellipsometry and constructed using 3D printing technology. The 3D-printed SPR module is user-friendly, durable, lightweight, and cost-effective, incorporating a flow cell crucial for liquid media operation. This integrated tool provides a highly surface-sensitive, non-invasive, and label-free optical sensing platform. The developed SPR-Ellipsometry platform demonstrates excellent performance in detecting biochemical analytes and multilayer adsorption of poly-electrolytes. The bulk refractive index sensitivity measurement was performed to calibrate the Au sensor chip. The Wavelength (SPR mode), amplitude (Ψ), and phase interrogation (∆) exhibit bulk refractive index sensitivities of 3098 ± 177 nm/RIU, 835 ± 22 °/RIU and 5839 ± 229 °/RIU, respectively. We obtained the refractive index resolution around 1.712 × 10−7 RIU. Protein-protein (BSA/Anti-BSA) interactions were also conducted, achieving a detection limit of 3 pM for Anti-BSA. This work will significantly expand the functionality of SPRE sensors by offering enhanced sensitivity, rich information, and high precision, as well as opening avenues for more efficient and accessible optical sensing technologies. Moreover, the study establishes a foundational framework for researchers, shedding light on the potential of 3D printers in laboratories and expediting the development of cost-effective integrated sensing platforms.

Low Fouling Polyelectrolyte Layer-by-Layer Self-Assembled Membrane for High Performance Dye/Salt Fractionation: Sequence Effect of Self-Assembly.

Layer-by-layer (LbL) self-assembly of oppositely charged polyelectrolytes (PEs) is usually performed on a conventional ultrafiltration base substrate (negative zeta potential) by depositing a cationic PE as a first layer. Herein, we report the facile and fast formation of high performance molecular selective membrane by the nonelectrostatic adsorption of anionic PE on the polyvinylidene fluoride (PVDF, zeta potential -17 mV) substrate followed by the electrostatic LbL assembly. Loose nanofiltration membranes have been prepared via both concentration-polarization (CP-LbL, under applied pressure) driven and conventional (C-LbL, dipping) LbL self-assembly. When the first layer is poly(styrene sodium) sulfonic acid, the LbL assembled membrane contains free -SO3- groups and exhibits higher rejection of Na2SO4 and lower rejection of MgCl2. The reversal of salt rejection occurs when the first layer is quaternized polyvinyl imidazole (PVIm-Me). The membrane (five layers) prepared by first depositing PStSO3Na shows higher rejection of several dyes (97.9 to >99.9%), higher NaCl to dye separation factor (52-1800), and higher dye antifouling performance as compared to the membrane prepared by first depositing PVIm-Me (97.5-99.5% dye rejection, separation factor ∼40-200). However, the C-LbL membrane requires a longer time of self-assembly or higher PE concentration to reach a performance close to the CP-LbL membranes. The membranes exhibit excellent pressure, pH (3-12), and salt (60 g L-1) stability. This work provides an insight for the construction of low fouling and high-performance membranes for the fractionation of dye and salt based on the LbL self-assembly sequence.

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.

Molecular insight into sequence-defined polyelectrolytes for energy storage devices

Polyelectrolyte (PE) adsorption on charged surfaces is a complex phenomenon that has an array of applications ranging from healthcare to designing energy storage devices. PE adsorption on surfaces involves surface charge polarization effects which arise due to the dielectric dissimilarities between the PE and the charged surface. PEs owing to their high potential window, and leakage-resistant behavior are used as supercapacitor electrolytes. Recent experimental evidence suggests co-block polymers as potential design materials for energy storage devices (ESDs). It is imperative to mention that the structural variation of the co-block polymers under spatial confinements will have a key role in designing electrodes and electrolytes for ESDs which demands a detailed investigation. This study reveals that the spatial orientations of the charged groups have an impressive impact on the changes in PE charge density peaks, charge amplification peaks, PE adsorption, counter-ion adsorption, and differential and integral capacitance while confined by graphene electrodes. It is startling to observe that the counter-ion distribution within the electrical double layer of the positively charged surface significantly depends on the orientation of the PEs. However, with increasing solvent dielectric constant the variations in the above-mentioned properties subside due to reduced electrostatic interactions. The differential capacitance and the integral capacitance are also found to be dependent on the dielectric constants of the solvent. These findings will be immensely useful in determining the key factors needed to describe the preferred spatial configuration of a PE suitable for various ESDs and applications involving PEs in a confined system.

Relative Strength of Polycation Adsorption on Oxide Surfaces.

Polyelectrolyte adsorption onto surfaces is widely employed in water treatment and mining. However, little is known of the relative interaction strengths between surfaces and polymer. This fundamental property is assumed to be dominated by electrostatics, i.e., attractive interactions between opposite charges, which are set by the overall ionic strength ("salt concentration") of the solution, and charge densities of the surface and the polymer. A common, counterintuitive finding is a range of salt concentrations over which the amount of adsorbed polyelectrolyte increases as electrostatic interactions are tempered by the addition of salt. After an adsorption maximum, higher salt concentrations then produce the expected gradual desorption of polyelectrolyte. In this work, the salt response of the adsorption of the same narrow molecular weight distribution polycation, poly(N-methyl-4-vinylpyridinium), PM4VP, to a variety of surfaces was explored. Oxide powders for adsorption included Al2O3, SiO2, Fe2O3, Fe3O4, TiO2, ZnO, and CuO. Planar surfaces included silicon wafers, mica, calcium carbonate, and CaF2 single crystals. The PM4VP was radiolabeled with 14C so that sensitive, submonolayer amounts could be detected. The position of the peak maximum, or the lack of a peak, in response to added salt was used to rank the electrostatic component of the interaction. The importance of charge regulation, a shift in the surface pKa in response to solution species, was highlighted as a mechanism for adsorption on the "wrong" side of the isoelectric point and also as a factor contributing to the difficulty of reaching the totally desorbed state even at the highest salt concentrations.

Mismatch and mix: Making use of electrokinetic aspects of spacers for intensified electrodialysis

Electrodialysis (ED) processes are limited in terms of practical current densities due to the emergence of concentration boundary layers. A great deal of research has focused on methods to promote mixing of these boundary layers, particularly through developing new spacers. Spacers are crucial to the performance of electrodialysis stacks, forming the flow channels between membranes and leading to hydrodynamic mixing that reduces mass transport limitations. Conventional analysis of spacers in ED has focused on characterizing the hydrodynamic mixing resulting from spacer geometry and assessing how this impacts the overall stack resistance. In this work, we explore the electrokinetic aspect of spacer performance: the electric-field bending induced by polymeric spacers and resulting electro-osmotic mixing. We carried out an experimental study to characterize the ED performance of a lab-scale stack using spacers with different surface charge densities, using polyelectrolyte adsorption on the spacers. Our results show that substantial increases in the current density or reductions in power consumption can be achieved when making use of this enhanced mixing due to electro-osmosis. We also explain this enhancement through the use of a simplified theoretical model to highlight the potential of utilizing electrokinetic mixing from spacers in electrodialysis.

INFUENCE OF ADSORPTION LAYERS OF POLYELECTROLYTES ON THE WETTING AND MODIFICATION OF THE POLYSTYRENE SURFACE

The adsorption of cationic and anionic polyelectrolytes from aqueous solutions on the polystyrene surface was studied by quartz crystal microbalance and contact angle measurements. It is shown that, despite the multilayer nature of adsorption, only a monolayer of polyelectrolyte macromolecules is rmly retained on the polymer surface, and the polystyrene surface is hydrophilized. It is shown that with complete monolayer lling of the surface, the degree of modi cation of the polystyrene surface does not depend on the nature of the studied polyelectrolytes, and the modifying monolayers provide the value of the polystyrene/water interfacial energy, which indicates the potential biocompatibility of the material based on the modi ed polystyrene.

Role of concentration and hydrophobic nature of weak polyelectrolytes on adsorption structure and thermodynamics at oil-water interface: Study of several carboxylate polymers

Intermolecular structure, conformations, solvation and adsorption characteristics of four partially ionized polycarboxylic acids syndiotactic-poly(acrylic acid) (s-PAA), syndiotactic-poly(methacrylic acid) (s-PMA), isotactic-poly(methacrylic acid) (i-PMA) and atactic-poly(ethacrylic acid) (a-PEA) at oil (CCl4) - water interface is studied by molecular dynamics simulations over the range from dilute to monolayer coverage. Linearity and slope of Θ-Γ curves are correlated to conformational invariance and extent of adsorption (partial vs complete) respectively, within the range of concentration of study. Adsorption of i-PMA and a-PEA chains occurs deeper into the oil-side of interface region as driven by the greater hydrophobicity of these polymers. Higher tendency of highly extended s-PMA to desorb from the interface as compared to strong adsorption of compact coiled i-PMA is driven by their solvation behavior dictated by aspects of structural partitioning of chemical groups with respect to the solvents of the two phases. Hydrophobic side-group in the polyelectrolyte chain is responsible for the slower dynamics of the backbone. The observed variation in thickness of adsorbed layer and fractional interface coverage with concentration suggest partial adsorption of chain segments beyond saturation of interface rather than coiling of chains to accommodate additional chains. While a-PEA exhibits greater variation in interfacial tension, the change in electric potential difference across the interface indicates weak adsorption by s-PMA. The influence of the tacticity of PMA on dynamics and distribution of counter-ions is in agreement with experimental results. Results provide a significant advancement in our understanding of polyelectrolyte and polymer adsorption at oil-water liquid interface.

A molecularly informed field-theoretic study of the complexation of polycation PDADMA with mixed micelles of sodium dodecyl sulfate and ethoxylated surfactants.

The self-assembly and phase separation of mixtures of polyelectrolytes and surfactants are important to a range of applications, from formulating personal care products to drug encapsulation. In contrast to systems of oppositely charged polyelectrolytes, in polyelectrolyte-surfactant systems the surfactants micellize into structures that are highly responsive to solution conditions. In this work, we examine how the morphology of micelles and degree of polyelectrolyte adsorption dynamically change upon varying the mixing ratio of charged and neutral surfactants. Specifically, we consider a solution of the cationic polyelectrolyte polydiallyldimethylammonium, anionic surfactant sodium dodecyl sulfate, neutral ethoxylated surfactants (C[Formula: see text]EO[Formula: see text]), sodium chloride salt, and water. To capture the chemical specificity of these species, we leverage recent developments in constructing molecularly informed field theories via coarse-graining from all-atom simulations. Our results show how changing the surfactant mixing ratios and the identity of the nonionic surfactant modulates micelle size and surface charge, and as a result dictates the degree of polyelectrolyte adsorption. These results are in semi-quantitative agreement with experimental observations on the same system.

Computer Simulation Insight into the Adsorption and Diffusion of Polyelectrolytes on Oppositely Charged Surface.

In the present work, by means of computer simulation, we studied the adsorption and diffusion of polyelectrolyte macromolecules on oppositely charged surfaces. We considered the surface coverage and the charge of the adsorbed layer depending on the ionization degree of the macromolecules and the charge of the surface and carried out a computer experiment on the polymer diffusion within the adsorbed layers, taking into account its strong dependency on the surface coverage and the macromolecular ionization degree. The different regimes were distinguished that provided maximal mobility of the polymer chains along with a high number of charged groups in the layer, which could be beneficial for the development of the functional coatings. The results were compared with those of previous experiments on the adsorption of polyelectrolyte layers that may be applied as biocidal renewable coatings that can reversibly desorb from the surface.

Rapid Quantitation of Various Therapeutic Monoclonal Antibodies Using Membranes with Fc-Specific Ligands.

Therapeutic monoclonal antibodies (mAbs) provide effective treatments for many diseases, including cancer, autoimmune disorders, and, lately, COVID-19. Monitoring the concentrations of mAbs is important during their production and subsequent processing. This work demonstrates a 5 min quantitation of most human immunoglobulin G (IgG) antibodies through capture of mAbs in membranes modified with ligands that bind to the fragment crystallizable (Fc) region. This enables binding and quantitation of most IgG mAbs. Layer-by-layer (LBL) adsorption of carboxylic acid-rich polyelectrolytes in glass-fiber membranes in 96-well plates allows functionalization of the membranes with Protein A or a peptide, oxidized Fc20 (oFc20), with high affinity for the Fc region of human IgG. mAb capture occurs in <1 min during the flow of solutions through modified membranes, and subsequent binding of a fluorophore-labeled secondary antibody enables quantitation of the captured mAbs using fluorescence. The intra- and inter-plate coefficients of variations (CV) are <10 and 15%, respectively, satisfying the acceptance criteria for many assays. The limit of detection (LOD) of 15 ng/mL is on the high end of commercial enzyme-linked immunosorbent assays (ELISAs) but certainly low enough for monitoring of manufacturing solutions. Importantly, the membrane-based method requires <5 minutes, whereas ELISAs typically take at least 90 min. Membranes functionalized with oFc20 show greater mAb binding and lower LODs than membranes with Protein A. Thus, the membrane-based 96-well-plate assay, which is effective in diluted fermentation broths and in mixtures with cell lysates, is suitable for near-real-time monitoring of the general class of human IgG mAbs during their production.

Adsorption kinetics of polyacrylamide-based polyelectrolyte onto a single silica particle studied using microfluidics and optical tweezers.

Polyelectrolyte adsorption is considered important in tuning the surface property and the fate of particles; however, often studied on macroscopic surfaces. To gain insights into how polyelectrolytes are adsorbed onto a single particle, it is imperative to utilize techniques capable of elucidating adsorption kinetics on a single-particle level in a controlled flow field. The polyelectrolyte adsorption kinetics was investigated by electrophoretic mobility measurements combined with the kinetics study onto a single-particle viewpoint using microfluidics and optical tweezers. We directly evaluated the thickness, δH, of adsorbed polyelectrolyte onto a negatively-charged silica particle to deduce the adsorbed polyelectrolyte's conformation. The effect of charge density and salt concentrations were studied. All polyelectrolytes exhibited dependence of δH on salt concentration. The attractive interactions control the cationic polyelectrolytes adsorption process. The δH depends on charge density indicating more loops and tail confirmation for the weakly-charged polyelectrolytes. The anionic polyelectrolytes showed a dependence of the initial rate and saturation value of δH on salt concentrations, attributed to the repulsion between charged segments and the silica surfaces. Here, we present new insights into the polyelectrolyte adsorption kinetics, particularly the influence of electrostatic interaction from the single-particle perspective, inaccessible to conventional bulk measurements.

Impact of polyelectrolyte adsorption on the rheology of concentrated poly(N-isopropylacrylamide) microgel suspensions.

We explore the impact of three water-soluble polyelectrolytes (PEs) on the flow of concentrated suspensions of poly(N-isopropylacrylamide) (PNIPAm) microgels with thermoresponsive anionic charge density. By progressively adding the PEs to a jammed suspension of swollen microgels, we show that the rheology of the mixtures is remarkably influenced by the sign of the PE charge, PE concentration and hydrophobicity only when the temperature is increased above the microgel volume phase transition temperature Tc, namely when microgels collapse, they are partially hydrophobic and form a volume-spanning colloidal gel. We find that the original gel is strengthened close to the isoelectric point, attained when microgels are mixed with cationic PEs, while PE hydrophobicity rules the gel strengthening at very high PE concentrations. Surprisingly, we find that polyelectrolyte adsorption or partial embedding of PE chains inside the microgel periphery occurs also when anionic polymers of polystyrene sulfonate with a high degree of sulfonation are added. This gives rise to colloidal stabilization and to the melting of the original gel network above Tc. Contrastingly, the presence of polyelectrolytes in suspensions of swollen, jammed microgels results in a weak softening of the original repulsive glass, even when an apparent isoelectric condition is met. Our study puts forward the crucial role of electrostatics in thermosensitive microgels, unveiling an exciting new way to tailor the flow of these soft colloids and highlighting a largely unexplored path to engineer soft colloidal mixtures.

Dye Adsorption of Surface Modified Cellulose Nanofibril Foams through Polyelectrolytes Multilayering

In this study, carboxymethylated cellulose nanofibril (CMCNF) foams were prepared through oven and freeze drying and chemically modified through the layer-by-layer (LbL) treatment of cationic (i.e., poly(diallyldimethylammonium chloride)) and anionic (i.e., poly(sodium 4-styrenesulfonate)) polyelectrolytes. The alternative adsorption of each polyelectrolyte on a CMCNF foam was confirmed by charge demand and Fourier transform infrared and energy-dispersive X-ray spectroscopic analyses. The cumulative adsorbed amount of polyelectrolytes in the freeze-dried foam increased up to two layers and reached a plateau, but the oven-dried foam exhibited a slower and gradual polyelectrolyte adsorption with the increasing layer number. The anionic dye adsorption was found superior when the cationic polyelectrolyte was adsorbed at the outermost layer of the CMCNF foam. The dye removal performance differed depending on the foam pore structure. Consequently, the surface charge of the CMCNF foam was effectively modified by the LbL treatment of polyelectrolytes, which can expand the application of the CMCNF foam in cationic or anionic dye removal.

Two different approaches to XPS quantitative analysis of polyelectrolyte adsorption layers

X‐ray photoelectron spectroscopy (XPS) was employed to quantify adsorption of polyelectrolytes from aqueous solutions of low ionic strength onto mica, glass, and silica. Silica surfaces were conditioned in base or in acid media as last pre‐treatment step (silica‐base last or silica‐acid last, respectively). Consistency in the determined adsorbed amount, Γ, was obtained independent of the choice of XPS mode and with the two quantification approaches used in the data evaluation. Under the same adsorption conditions, the adsorbed amount, Γ, varied as Γmica &gt; Γsilica‐base last ≈ Γglass &gt; Γsilica‐acid last. In addition, the adsorbed amount increased with decreasing polyelectrolyte charge density (100% to 1% of segments being charged) for all substrates. Large adsorbed amount was measured for low‐charge density polyelectrolytes, but the number of charged segments per square nanometer was low due to steric repulsion between polyelectrolyte chains that limited the adsorption. The adsorbed amount of highly charged polyelectrolytes was controlled by electrostatic interactions and thus limited to that needed to neutralize the substrate surface charge density. For silica, the adsorbed amount depended on the cleaning method, suggesting that this process influenced surface concentration and fraction of different silanol groups. Our results demonstrate that for silica, a higher density and/or more acidic silanol groups are formed using base, rather than acid, treatment in the last step.

The comparison of adsorption kinetics of polystyrene particles with two polyelectrolytes near the isoelectric points

Microplastics are widely regarded as an emerging pollution owing to ubiquitous environmental distributions and toxicological characteristics. The adsorption kinetics of microplastic particles with polyelectrolytes is vital to improve the removal efficiency of microplastics, however, the adsorption kinetics of polyelectrolytes onto the particle surface is far from well understood near the isoelectric point. The adsorption of high and low charge density polyelectrolytes was investigated near the isoelectric point based on the measurement of the electrophoretic mobility. The mobility of particles adsorbing high charge density polyelectrolytes reaches the plateau in several seconds, whereas low charge density polyelectrolyte takes about dozens of seconds to reach the plateau of zero. The adsorption of high charge density polyelectrolyte is enhanced with the decrease of ionic strength, whereas, low charge density polyelectrolyte demonstrates the opposite tendency against ionic strength. All results will facilitate the analysis of the flocculation process of microplastic particles.

Self-assembled archaea bio-coatings in thermal-fluids systems: A study on adhesion optimization and energy efficiency

In this study, adhesion optimization was performed for archaea bio-coatings to be used in thermal-fluids systems. For this, Sulfolobus Solfataricus P2 archaea was coated onto silicon wafer substrate surfaces by polyelectrolyte adhesive layers made of Poly-l-Lysine and Poly-l-Arginine. Polyelectrolyte adsorption is a self-assembling phenomenon where the oppositely charged layers are electrostatically attracted to each other. We herein report the coating performance of samples prepared with two different coating methodologies: Layer-by-Layer and mixed coating. Samples were optimized with respect to thickness and durability by varying the polyelectrolyte concentration, salt concentration, and mixture ratios. A closed loop system was prepared to test the durability of the coated samples against fluid flow, and Atomic Force Microscopy and Surface Profilometer techniques were utilized to characterize the topology and thickness of the samples before and after each test. The results reveal the existence of an optimal configuration for the mixed coated samples, where adding excess charged groups shifted the force balance to either the negative or positive side, decreasing adhesion in both cases. Increasing the ionic strength of the solution resulted in 17% and 20% increases in coating thickness for PLL and PLA samples, respectively. However, in some cases, samples appeared to have worsened durability. After the durability tests, the samples were used to evaluate the heat transfer performance of the coatings in a real thermal-fluids system. The obtained results show enhancements more than 20% in boiling heat transfer.

Two Sides of the Same Coin: A Unified Theoretical Treatment of Polyelectrolyte Complexation in Solution and Layer-by-Layer Films

Polyelectrolyte coacervates, obtained by mixing solutions of oppositely charged polyions, and layer-by-layer films, produced by sequential adsorption of polyelectrolytes on a surface, are two types of closely related soft materials. While both types of materials are produced by polyelectrolyte complexation, their theoretical description had so far followed divergent paths. This work reports a unifying theoretical treatment of polyelectrolyte complexation in solution and layer-by-layer self-assembled thin films using a molecular theory that describes polyelectrolyte complexation by using a chemical-equilibrium formalism. The theory is shown to predict both the phase diagrams of polyelectrolyte mixtures in solution and the formation of layer-by-layer thin films in good agreement with experimental evidence. In the latter case, the theory correctly captures the effects of solution pH and ionic strength on the mass of the deposited films as well as the possibility of layer-by-layer deposition without full charge reversal at extreme pHs. The theory is then used to revisit the “universal curve” for the effect of salt concentration on layer-by-layer deposition previously proposed on experimental grounds by Salehi et al. [Macromolecules 2015, 48, 400–409]. This universal curve makes predictions about the growth rate of a layer-by-layer film for a given polyanion/polycation pair by using only information obtained from a mixture of the same polyelectrolytes in solution, thereby linking both phenomena. Our theoretical results confirm the validity of the curve. This achievement demonstrates the practical importance of describing polyelectrolyte coacervates and multilayer films within a unified theoretical framework.