Formation Of Polyelectrolyte Multilayers Research Articles

Interfacial rheology of linearly growing polyelectrolyte multilayers at the water-air interface: from liquid to solid viscoelasticity.

Despite the long history of investigations of polyelectrolyte multilayer formation on solid or liquid surfaces, important questions remain open concerning the construction of the first set of layers. These are generally deposited on a first anchoring layer of different chemistry, influencing their construction and properties. We propose here an in-depth investigation of the formation of NaPSS/PAH multilayers at the air/water interface in the absence of a chemically different anchoring layer, profiting from the surface activity of NaPSS. To analyse the mechanical properties of the different layers, we combine recently established analysis techniques of an inflating/deflating bubble exploiting simultaneous shape and pressure measurement: bubble shape elastometry, general stress decomposition and capillary meniscus dynanometry. We complement these measurements by interfacial shear rheology. The obtained results allow us to confirm, first of all, the strength of the aforementioned techniques to characterize complex interfaces with non-linear viscoelastic properties. Furthermore, their sensitivity allows us to show that the multilayer properties are highly sensitive to the temporal and mechanical conditions under which they are constructed and manipulated. We nevertheless identify a robust trend showing a clear transition from a liquid-like viscoelastic membrane to a solid-like viscoelastic membrane after the deposition of 5 layers. We interpret this as the number of layers required to create a fully connected multilayer, which is consistent with previous results obtained on solid or liquid interfaces.

Expanding the Scope of an Amphoteric Condensed Tannin, Tanfloc, for Antibacterial Coatings.

Bacterial infections are a common mode of failure for medical implants. This study aims to develop antibacterial polyelectrolyte multilayer (PEM) coatings that contain a plant-derived condensed tannin polymer (Tanfloc, TAN) with inherent antimicrobial activity. Tanfloc is amphoteric, and herein we show that it can be used as either a polyanion or a polycation in PEMs, thereby expanding the possibility of its use in PEM coatings. PEMs are ordinarily formed using a polycation and a polyanion, in which the functional (ionic) groups of the two polymers are complexed to each other. However, using the amphoteric polymer Tanfloc with weakly basic amine and weakly acidic catechol and pyrogallol groups enables PEM formation using only one or the other of its functional groups, leaving the other functional group available to impart antibacterial activity. This work demonstrates Tanfloc-containing PEMs using multiple counter-polyelectrolytes including three polyanionic glycosaminoglycans of varying charge density, and the polycations N,N,N-trimethyl chitosan and polyethyleneimine. The layer-by-layer (LbL) assembly of PEMs was monitored using in situ Fourier-transform surface plasmon resonance (FT-SPR), confirming a stable LbL assembly. X-ray photoelectron spectroscopy (XPS) was used to evaluate surface chemistry, and atomic force microscopy (AFM) was used to determine the surface roughness. The LDH release levels from cells cultured on the Tanfloc-containing PEMs were not statistically different from those on the negative control (p > 0.05), confirming their non-cytotoxicity, while exhibiting remarkable antiadhesive and bactericidal properties against Pseudomonas aeruginosa (P. aeruginosa) and Staphylococcus aureus (S. aureus), respectively. The antibacterial effects were attributed to electrostatic interactions and Tanfloc's polyphenolic nature. This work underscores the potential of Tanfloc as a versatile biomaterial for combating infections on surfaces.

Surface properties and bioactivity of PNIPAM-grafted-chitosan/chondroitin multilayers

The thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) is widely applied in the biomedical field particularly as thermoresponsive substrate for culture of cells. To be used as a stimuli-responsive coating for cell culture, combining PNIPAM with glycosaminoglycans might be an effective approach to improve its bioactivity. In this study, chitosan is grafted with PNIPAM moieties (PCHI) possessing a cloud point at 31 ​°C and used as a polycation to fabricate thermoresponsive polyelectrolyte multilayers (PEM) with the bioactive polyanion chondroitin sulfate (CS) at pH 4 by layer-by-layer technique. The in-situ investigation by surface plasmon resonance and quartz crystal microbalance with dissipation monitoring confirms that the formation of PEMs with CS can be achieved despite the bulky structure of PCHI at 25 ​°C. The stability of the PEMs is further improved at physiological pH 7.4 by chemical crosslinking using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide. Moreover, these PEMs exhibit de-swelling and swelling ability with different surface wettability in response to temperature, which triggers the adsorption and desorption of adhesive protein vitronectin on the PEMs. At 37 ​°C, the PEMs containing PNIPAM particularly associated with CS terminal layer supports protein adsorption and consequently enhances cell adhesion using multipotent murine stem cells. Overall, due to improved stability, crosslinked PNIPAM-modified biogenic multilayers are cytocompatible and hold great potential as culture substrate for different tissue cells and application in tissue engineering.

Stability of Biomimetically Functionalised Alginate Microspheres as 3D Support in Cell Cultures.

Alginate hydrogels can be used to develop a three-dimensional environment in which various cell types can be grown. Cross-linking the alginate chains using reversible ionic bonds opens up great possibilities for the encapsulation and subsequent release of cells or drugs. However, alginate also has a drawback in that its structure is not very stable in a culture medium with cellular activity. This work explored the stability of alginate microspheres functionalised by grafting specific biomolecules onto their surface to form microgels in which biomimetic microspheres surrounded the cells in the culture, reproducing the natural microenvironment. A study was made of the stability of the microgel in different typical culture media and the formation of polyelectrolyte multilayers containing polylysine and heparin. Multiple myeloma cell proliferation in the culture was tested in a bioreactor under gentle agitation.

Polyelectrolyte Complexation When Considering the Counterion-Mediated Hydrogen Bonding.

In this work, we have investigated a pH-modulated complexation between two oppositely charged strong polyelectrolytes to demonstrate the effect of counterion-mediated hydrogen bonding (CMHB) on polyelectrolyte complexation. We have found that such a pH-modulated complexation cannot be understood without considering the CMHB. Thermodynamically, the effect of CMHB on the polyelectrolyte complexation is manifested by the alteration of both enthalpic and entropic contributions to the free energy change. The pH-dependent intrinsic ion-pairing and complex coacervation processes of the polyelectrolyte complexation can be understood when considering the CMHB. Our study demonstrates that both the extent of polyelectrolyte complex formation in bulk solutions and the formation of polyelectrolyte multilayers on surfaces are controlled by the pH-dependent intrinsic ion-pairing process. Furthermore, on the basis of the pH-dependent intrinsic ion pairing, the properties of the multilayers can be tuned by pH. This work provides a new strategy to control the polyelectrolyte complexation with counterions and will inspire new ideas for building advanced polyelectrolyte materials.

Role of Substrate Type in the Process of Polyelectrolyte Multilayer Formation.

Polyelectrolyte multilayers are coatings formed by the alternate deposition of polycations and polyanions on a charged surface. In this study we examined how the type of substrate affects a multilayer prepared from poly(allylamine hydrochloride) and poly(acrylic acid). Silicon and titanium wafers were used as substrates. Their properties were systematically studied using ellipsometry, tensiometry, atomic force microscopy and streaming potential measurements. Multilayers were built up at pH = 7 with tetramethylammonium chloride as the background salt. The growth of films was monitored by ellipsometry, while the morphology and surface roughness were determined by atomic force microscopy. It was found that the thickness of multilayers containing 10 layers on silicon is 10 nm, whereas the thickness of the same film on titanium is three times higher. It was shown that multilayers formed on silicon display a grain-like structure, which was not the case for a film formed on titanium. Such morphological properties are also reflected in the surface roughness. Finally, it was shown that, in addition to the electrostatic interactions, the hydrophobicity of the substrate also plays an important role in the polyelectrolyte multilayer formation process and influences its thickness and properties.

Predicting the outcomes of interpolyelectrolyte neutralization at surfaces on the basis of complexation experiments and vice versa.

This study was carried out with the aim of establishing how the outcomes of polyelectrolyte multilayer formation can be predicted on the basis of the results of complexation studies in solution and vice versa. For this purpose, the correlation between the processes of complex and multilayer formation involving three pairs of vinylic polyions in solutions of binary 1 : 1 sodium salts (NaX; X = F, Cl, Br, I, NO3, ClO4) was explored by means of dynamic and electrophoretic light scattering, potentiometry, microcalorimetry, spectrophotometry and quartz crystal microbalance. The gradual reactant mixing in solution at lower salt concentrations resulted in a Fuoss-Sadek sequence of events (primary complexes → secondary complexes → 1 : 1 flocculate), whereby the obtained nano-complexes could be successively overcharged. At high salt concentration and with excess polycation present, metastable nano-complexes and precipitates containing surplus of positively charged monomers were formed. The amount of extrinsically compensated charge was in accord with the polycation affinities toward counteranions, established by monitoring the electrolyte-induced aggregation of positively charged nano-complexes. Perfect analogy with respect to counteranion influence on the amount of adsorbed polycation was noticed for corresponding multilayers. Aside from providing a deeper understanding of interpolyelectrolyte neutralization, the gained insights can also be used to steer the polyelectrolyte multilayer composition and properties.

Polyelectrolyte multilayer formation on protein layer supports

Polyelectrolyte multilayers (PEMs) have been intensively studied as a straightforward means to modify surfaces for a variety of applications. Their study using advanced tools of interfacial science has underpinned their potential as surface coatings, however, this degree of characterisation is greater for PEMs on solid substrates. The formation of multilayers on soft/deformable interfaces is not so heavily studied, and to a great extent the formation characteristics are simply assumed. In this work, we have studied comparatively the formation of a polyelectrolyte multilayer on both a solid support and upon a pre-adsorbed layer of a protein (β-lactoglobulin – BLG). The study of a protein support for PEMs is a useful intermediate step between a solid support and truly deformable interfaces (such as the air-water or oil-water interface). Our investigation has revealed that, compared to build-up on a solid support, a polyelectrolyte multilayer formed from polydiallyldimethylammonium chloride (PDADMAC) and poly(sodium styrene sulfonate) (PSS) on a pre-adsorbed layer of BLG displays more regular growth from the very first layer, with overall higher mass deposited. The protein-supported film also displays more regular outer layer effects (in this case mechanical properties), at an earlier stage of build-up. For applications that require relatively thin PEMs, the use of a soft cushion support as an initial layer may produce better coatings.

Model Surfaces for Paper Fibers Prepared from Carboxymethyl Cellulose and Polycations.

For tailored functionalization of cellulose based papers, the interaction between paper fibers and functional additives must be understood. Planar cellulose surfaces represent a suitable model system for studying the binding of additives. In this work, polyelectrolyte multilayers (PEMs) are prepared by alternating dip-coating of the negatively charged cellulose derivate carboxymethyl cellulose and a polycation, either polydiallyldimethylammonium chloride (PDADMAC) or chitosan (CHI). The parameters varied during PEM formation are the concentrations (0.1–5 g/L) and pH (pH = 2–6) of the dipping solutions. Both PEM systems grow exponentially, revealing a high mobility of the polyelectrolytes (PEs). The pH-tunable charge density leads to PEMs with different surface topographies. Quartz crystal microbalance experiments with dissipation monitoring (QCM-D) reveal the pronounced viscoelastic properties of the PEMs. Ellipsometry and atomic force microscopy (AFM) measurements show that the strong and highly charged polycation PDADMAC leads to the formation of smooth PEMs. The weak polycation CHI forms cellulose model surfaces with higher film thicknesses and a tunable roughness. Both PEM systems exhibit a high water uptake when exposed to a humid environment, with the PDADMAC/carboxymethyl cellulose (CMC) PEMs resulting in a water uptake up to 60% and CHI/CMC up to 20%. The resulting PEMs are water-stable, but water swellable model surfaces with a controllable roughness and topography.

Chitosan-miRNA functionalized microporous titanium oxide surfaces via a layer-by-layer approach with a sustained release profile for enhanced osteogenic activity

BackgroundThe biofunctionalization of titanium implants for high osteogenic ability is a promising approach for the development of advanced implants to promote osseointegration, especially in compromised bone conditions. In this study, polyelectrolyte multilayers (PEMs) were fabricated using the layer-by-layer approach with a chitosan-miRNA (CS-miRNA) complex and sodium hyaluronate (HA) as the positively and negatively charged polyelectrolytes on microarc-oxidized (MAO) Ti surfaces via silane-glutaraldehyde coupling.MethodsDynamic contact angle and scanning electron microscopy measurements were conducted to monitor the layer accumulation. RiboGreen was used to quantify the miRNA loading and release profile in phosphate-buffered saline. The in vitro transfection efficiency and the cytotoxicity were investigated after seeding mesenchymal stem cells (MSCs) on the CS-antimiR-138/HA PEM-functionalized microporous Ti surface. The in vitro osteogenic differentiation of the MSCs and the in vivo osseointegration were also evaluated.ResultsThe surface wettability alternately changed during the formation of PEMs. The CS-miRNA nanoparticles were distributed evenly across the MAO surface. The miRNA loading increased with increasing bilayer number. More importantly, a sustained miRNA release was obtained over a timeframe of approximately 2 weeks. In vitro transfection revealed that the CS-antimiR-138 nanoparticles were taken up efficiently by the cells and caused significant knockdown of miR-138 without showing significant cytotoxicity. The CS-antimiR-138/HA PEM surface enhanced the osteogenic differentiation of MSCs in terms of enhanced alkaline phosphatase, collagen production and extracellular matrix mineralization. Substantially enhanced in vivo osseointegration was observed in the rat model.ConclusionsThe findings demonstrated that the novel CS-antimiR-138/HA PEM-functionalized microporous Ti implant exhibited sustained release of CS-antimiR-138, and notably enhanced the in vitro osteogenic differentiation of MSCs and in vivo osseointegration. This novel miRNA-functionalized Ti implant may be used in the clinical setting to allow for more effective and robust osseointegration.

Layer-By-Layer Assemblies of Biopolymers: Build-Up, Mechanical Stability and Molecular Dynamics.

Rapid development of versatile layer-by-layer technology has resulted in important breakthroughs in the understanding of the nature of molecular interactions in multilayer assemblies made of polyelectrolytes. Nowadays, polyelectrolyte multilayers (PEM) are considered to be non-equilibrium and highly dynamic structures. High interest in biomedical applications of PEMs has attracted attention to PEMs made of biopolymers. Recent studies suggest that biopolymer dynamics determines the fate and the properties of such PEMs; however, deciphering, predicting and controlling the dynamics of polymers remains a challenge. This review brings together the up-to-date knowledge of the role of molecular dynamics in multilayers assembled from biopolymers. We discuss how molecular dynamics determines the properties of these PEMs from the nano to the macro scale, focusing on its role in PEM formation and non-enzymatic degradation. We summarize the factors allowing the control of molecular dynamics within PEMs, and therefore to tailor polymer multilayers on demand.

Dual Monitoring of Surface Reactions in Real Time by Combined Surface-Plasmon Resonance and Field-Effect Transistor Interrogation.

By combining surface plasmon resonance (SPR) and electrolyte gated field-effect transistor (EG-FET) methods in a single analytical device we introduce a novel tool for surface investigations, enabling simultaneous measurements of the surface mass and charge density changes in real time. This is realized using a gold sensor surface that simultaneously serves as a gate electrode of the EG-FET and as the SPR active interface. This novel platform has the potential to provide new insights into (bio)adsorption processes on planar solid surfaces by directly relating complementary measurement principles based on (i) detuning of SPR as a result of the modification of the interfacial refractive index profile by surface adsorption processes and (ii) change of output current as a result of the emanating effective gate voltage modulations. Furthermore, combination of the two complementary sensing concepts allows for the comparison and respective validation of both analytical techniques. A theoretical model is derived describing the mass uptake and evolution of surface charge density during polyelectrolyte multilayer formation. We demonstrate the potential of this combined platform through the observation of layer-by-layer assembly of PDADMAC and PSS. These simultaneous label-free and real-time measurements allow new insights into complex processes at the solid-liquid interface (like non-Fickian ion diffusion), which are beyond the scope of each individual tool.

Layer-by-layer Multilayered Film Formation on Gradient Polyelectrolyte Brush Prepared by Bipolar Electrochemistry

Polyelectrolyte multilayer formation on a gradient polymer brush was investigated for the first time. The gradient anionic polyelectrolyte brush was synthesized by combining bipolar electrochemistr...

Surface Forces of Asymmetrically Grown Polyelectrolyte Multilayers: Searching for the Charges.

Surface forces are used to investigate the polymer conformation and the surface charge of polyelectrolyte multilayers. Films are prepared from strong polyelectrolytes with low and high linear charge density at 0.1 M NaCl, namely poly(diallyldimethylammonium) (PDADMA) and poly(styrenesulfonate) (PSS). The multilayer has two growth regimes: in the beginning, the film can contain as many positive as negative monomers. After about 15 deposited layer pairs, a linear growth regime characterized by an excess of cationic PDADMA monomers occurs. Independent of the film composition, at preparation conditions, the film surface is flat, uncharged and partially hydrophobic. Surface force measurements at decreased ionic strength provide insight. For PSS-terminated films electrostatic forces are found. At the beginning of multilayer formation, the surface charge density is negative. However, in the linear growth regime it is positive and low (one charge per 200-400 nm2). This reversal of surface charge density of PSS-terminated films is attributed to excess PDADMA-monomers within the film. PDADMA terminated films show steric forces, chains protrude into the solution and form a pseudobrush, which scales as a polyelectrolyte brush with a low grafting density (1900 nm2 per chain). We suggest a model of polyelectrolyte multilayer formation: PDADMA with its low linear charge density adsorbs with weakly bound chains. Monovalent anions within the film compensate PDADMA monomer charges. When PSS adsorbs onto a PDADMA-terminated multilayer, PSS monomers replace monovalent anions. While electrostatic bonds are formed and dissolved within the polyelectrolyte multilayer, the surface charge density remains zero.

Two types of polyelectrolyte multilayers hydrogel membrane based on chitosan and alginate with different self-assembled process for control L929 cell behavior

Controlling the adhesion of mammalian cells at the interface between materials and biological environments is a real challenge when designing materials for tissue engineering applications. The surface properties of implanted materials are known to have a significant impact on cell adhesion. Herein, two types of polyelectrolyte multilayers (PEMs) hydrogel membrane based on marine-derived polysaccharides of chitosan (CHI) and alginate (ALG) biopolymers were fabricated by the layer-by-layer (LbL) technique using simple approach involving the change in assemble sequence of chitosan with different degree of deacetylation (DD). The effect of PEMs formation on the surface properties and their effects on the adhesion of mouse fibroblast cell (L929) of the two membranes were studied. The results showed that the formations of ALG/CHI membranes were related to the rigidity and conformations of chitosan molecules. The adhesion of L929 cell was strongly depended on the surface roughness rather than stiffness. The surface of PEMs can be strongly cytophilic (cell adhesive, terminated with chitosan (C1)) or strongly cytophobic (cell resistant, terminated with chitosan (C2)). The results obtained indicate that ALG/CHI PEMs with different surface morphology and roughness could be used in vitro to manipulate cell behaviors to improve upon the design of tissue-engineered membranes.

Fabrication of self-assembled polysaccharide multilayers on broke chemi-mechanical pulp fibers: Effective approach for paper strength enhancement

The present study was conducted to form polysaccharide-based multilayers of cationic starch (CS)/anionic starch (AS), and CS/carboxymethyl cellulose (CMC) on broke chemi-mechanical pulp (BCMP) fibers. It aimed to examine the buildup of CS/AS and CS/CMC polyelectrolyte multilayers (PEM) on the fibers surface, and explore the effects of PEM formation on the properties of the resulting papers. The assembly of PEM was analyzed by using zeta (ζ-) potential, water retention value (WRV), SEM micrographs, and paper properties such as thickness and strength. The results of ζ-potential inversions indicated successful constitution of PEM on the BCMP fiber surface by assembling CS/AS or CS/CMC multilayers. Further, larger ζ-potential variations occurred in depositing CS/CMC PEM, due to more charge of CMC, which presumably formed a layer with greater potential of absorption. Based on the SEM images, the surface of PEM-treated fibers was rougher, compared to the untreated fibers due to the coating with starch. Furthermore, the PEM fabrication resulted in creating fibers with higher degree of WRV, which was consistent with the significant improvement of the sheet strengths. Finally, the strength enhanced papers made from PEM-treated fibers with tensile index of about 37.33 ± 1.47 N m/g vs 22.24 ± 1.23 N m/g or 11.60 ± 0.57 N m/g for the papers made from original CMP and untreated BCMP fibers, respectively, may diminish the challenges related to web breaks in the paper machine conveying BCMP broke fibers.

Effect of Polyelectrolyte Mono- and Bilayer Formation on the Colloidal Stability of Layered Double Hydroxide Nanoparticles.

Sequential adsorption of polyelectrolytes on nanoparticles is a popular method to obtain thin films after deposition. However, the effect of polyelectrolyte multilayer formation on the colloidal stability of the nanoparticles has not been studied in detail. In the present work, layered double hydroxides (LDH) were synthesized and interaction with oppositely and like-charged polyelectrolytes was investigated. Electrophoretic and light scattering measurements revealed that colloidal stability of LDH can be tuned by adsorption of poly(styrene sulfonate) (PSS) on the oppositely charged LDH surface in appropriate doses and thus, unstable or stable dispersions can be designed. Negatively charged LDH of adsorbed PSS monolayer was obtained and a poly(diallyldimethyl ammonium chloride) (PDADMAC) second layer was systematically built on the particles. The obtained polyelectrolyte bilayer provided high colloidal stability for the LDH-PSS-PDADMAC dispersions due to the presence of repulsive interparticle forces of electrostatic and steric origin. The results provide crucial quantitative information on designing highly stable particle-polyelectrolyte systems for the preparation of thin films or immobilization of guest substances between the layers for delivery processes.

Multilayer assembly of ionic starches on old corrugated container recycled cellulosic fibers

AbstractIn this study, old corrugated container recycled fibers were treated with polyelectrolyte multilayers consisting of biopolymer cationic starch with two degrees of substitution (DS) each in combination with one anionic starch. Pulp zeta potential, paper strength and the thin layer ellipsometry technique were applied to examine the influence of cationic starch DS on the formation of polyelectrolyte multilayers. The results indicated a significant interaction between the DS of cationic starch and the number of ionic starch layers formed. When low‐DS cationic starch was used, the pulp zeta potential and the paper strength increased significantly in assembling the first cationic layer. However, in depositing high‐DS cationic starch a greater zeta potential and a stronger influence on the paper strength were observed with a larger number of starch layers. This was confirmed by thin layer ellipsometry when a greater thickness of multilayers was achieved by employing high‐DS cationic starch to form a higher number of layers. © 2017 Society of Chemical Industry

Influence of Surface Charge Density and Morphology on the Formation of Polyelectrolyte Multilayers on Smooth Charged Cellulose Surfaces.

To clarify the importance of the surface charge for the formation of polyelectrolyte multilayers, layer-by-layer (LbL) assemblies of polydiallyldimethylammonium chloride (pDADMAC) and polystyrenesulfonate (PSS) have been investigated on cellulose films with different carboxylic acid contents (20, 350, 870, and 1200 μmol/g) regenerated from oxidized cellulose. The wet cellulose films were thoroughly characterized prior to multilayer deposition using quantitative nanomechanical mapping (QNM), which showed that the mechanical properties were greatly affected by the degree of oxidation of the cellulose. Atomic force microscopy (AFM) force measurements were used to determine the surface potential of the cellulose films by fitting the force data to the DLVO theory. With the exception of the 1200 μmol/g film, the force measurements showed a second-order polynomial increase in surface potential with increasing degree of oxidation. The low surface potential for the 1200 μmol/g film was attributed to the low degree of regeneration of the cellulose film in aqueous media due to increasing solubility with increasing charge. The multilayer formation was characterized using a quartz crystal microbalance with dissipation (QCM-D) and stagnation-point adsorption reflectometry (SPAR). Extensive deswelling was observed for the charged films when pDADMAC was adsorbed due to the reduced osmotic pressure when ions inside the film were released, and the 1:1 charge compensation showed that all the charges in the films were reached by the pDADMAC. The multilayer formation was not significantly affected by the charge density above 350 μmol/g due to interlayer repulsions, but it was strongly affected by the salt concentration during the layer build-up.

From polyelectrolyte complexes to polyelectrolyte multilayers: Electrostatic assembly, nanostructure, dynamics, and functional properties

Polyelectrolyte complexes (PECs) are three-dimensional macromolecular structures formed by association of oppositely charged polyelectrolytes in solution. Polyelectrolyte multilayers (PEMs) can be considered a special case of PECs prepared by layer-by-layer (LbL) assembly that involves sequential deposition of molecular-thick polyelectrolyte layers with nanoscale control over the size, shape, composition and internal organization. Although many functional PEMs with novel physical and chemical characteristics have been developed, the current practical applications of PEMs are limited to those that require only a few bilayers and are relatively easy to prepare. The viability of such engineered materials can be realized only after overcoming the scientific and engineering challenges of understanding the kinetics and transport phenomena involved in the multilayer growth and the factors governing their final structure, composition, and response to external stimuli. There is a great need to model PEMs and to connect PEM behavior with the characteristics of the PEC counterparts to allow for prediction of performance and better design of multilayered materials. This review focuses on the relationship between PEMs and PECs. The constitutive interactions, the thermodynamics and kinetics of polyelectrolyte complexation and PEM formation, PEC phase behavior, PEM growth, the internal structure and stability in PEMs and PECs, and their response to external stimuli are presented. Knowledge of such interactions and behavior can guide rapid fabrication of PEMs and can aid their applications as nanocomposites, coatings, nano-sized reactors, capsules, drug delivery systems, and in electrochemical and sensing devices. The challenges and opportunities in future research directions are also discussed.