Weak Polyelectrolytes as Nanoarchitectonic Design Tools for Functional Materials: A Review of Recent Achievements.

The ionization degree, charge density, and conformation of weak polyelectrolytes can be adjusted through adjusting the pH and ionic strength stimuli. Such polymers thus offer a range of reversible interactions, including electrostatic complexation, H-bonding, and hydrophobic interactions, which position weak polyelectrolytes as key nano-units for the design of dynamic systems with precise structures, compositions, and responses to stimuli. The purpose of this review article is to discuss recent examples of nanoarchitectonic systems and applications that use weak polyelectrolytes as smart components. Surface platforms (electrodeposited films, brushes), multilayers (coatings and capsules), processed polyelectrolyte complexes (gels and membranes), and pharmaceutical vectors from both synthetic or natural-type weak polyelectrolytes are discussed. Finally, the increasing significance of block copolymers with weak polyion blocks is discussed with respect to the design of nanovectors by micellization and film/membrane nanopatterning via phase separation.

Analytical strategy for studying the formation and stability of multilayered films containing gold nanoparticles.

The design of layer-by-layer (LbL) polyelectrolyte films including nanoparticles is a growing field of innovation in a wide range of biomedical applications. Gold nanoparticles (AuNPs) are very attractive for further biomolecule coupling to induce a pharmacological effect. Nanostructured LbL films coupled with such metallic species show properties that depend on the conditions of construction, i.e. the polymer nature and dissolution buffer. Tripartite LbL films (polycation, AuNP, and polyanion) were evaluated using two different polycationic polymers (poly(allylamine hydrochloride) (PAH), poly(ethylene imine) (PEI)) and various medium conditions (salts, i.e. phosphate, Tris or Tris-NaCl buffers, and concentration). AuNP incorporation and film stability were analysed by visible spectrophotometry, capillary zone electrophoresis, a quartz crystal microbalance, and high-performance liquid chromatography. The ideal compromise between AuNP loading and film stability was obtained using PAH prepared in Tris-NaCl buffer (0.01-0.15 M). This condition allowed the formation of a LbL film that was more stable than the film with PEI and provided an AuNP quantity that was 4.8 times greater than that of the PAH-PBS-built film. In conclusion, this work presents an analytical strategy for the characterization of nanostructured multilayer films and optimization of LbL films enriched with AuNPs to design biomedical device coatings.

Controlling Structural Transformation of Polyelectrolyte Films for Spatially Encapsulating Functional Species.

Although many approaches have been developed to encapsulate functional species into polyelectrolyte films, few of them can effectively control the final distribution of these ones. Herein, a facile strategy is proposed to spatially control the encapsulation of guest species by locally regulating the structural transformation of polyelectrolyte films. Patterned porosity is created within a film by cross-linking it selectively and then immersing it in an acidic solution. These porous regions can exhibit significantly different properties from other regions, including the ability to wick solution, a greater retention of guest species, and the capability of structural transformation. After loading guest species, the porous structures can be eliminated at saturated humidity to encapsulate the guest species into the film, leading to their patterned distribution across the film. Based on this method, various guest species, ranging from fluorescent dyes to nanoparticles, can be locally encapsulated into polyelectrolyte film, forming distinct patterns of arbitrary shapes and sizes and thus paving the way for further applications.

Humidity-Triggered Relaxation of Polyelectrolyte Complexes as a Robust Approach to Generate Extracellular Matrix Biomimetic Films.

Generating a biofunctional film that can mimic the extracellular matrix (ECM) in an efficient and robust technique that may have great potential for medical devices, tissue engineering, and regenerative medicines. Herein, a facile approach to generate ECM biomimetic films based on the humidity-triggered relaxation of polyelectrolyte complex (PEC) nanoparticles is reported. The poly(l-lysine) and hyaluronan are precomplexed and sprayed onto a substrate, which, via a trigger of vaporous water, can be transformed into an even and stable film. The spontaneous polymer chain interfusion (diffusion coefficient ≈1.01 × 10-9  cm2  s-1 ) under saturated humidity, allowing for the rapid reorganization (within 30 min) of film morphology and structure is demonstrated. A controllable and scalable way for the loading of diversified bioactive agents, as well as on-demand modulation of stiffness is further presented. Moreover, the high-throughput arrays and programmed patterns can be easily completed, suggesting huge potentials that surpass those of state-of-the-art methods. Combined with high efficiency and flexible functionalization, it is believed that this approach should be beneficial for extending the practical applications of PEC films, such as medical implants, chip detectors, and so on.

Recent Progress and Perspectives in the Electrokinetic Characterization of Polyelectrolyte Films.

The analysis of the charge, structure and molecular interactions of/within polymeric substrates defines an important analytical challenge in materials science. Accordingly, advanced electrokinetic methods and theories have been developed to investigate the charging mechanisms and structure of soft material coatings. In particular, there has been significant progress in the quantitative interpretation of streaming current and surface conductivity data of polymeric films from the application of recent theories developed for the electrohydrodynamics of diffuse soft planar interfaces. Here, we review the theory and experimental strategies to analyze the interrelations of the charge and structure of polyelectrolyte layers supported by planar carriers under electrokinetic conditions. To illustrate the options arising from these developments, we discuss experimental and simulation data for plasma-immobilized poly(acrylic acid) films and for a polyelectrolyte bilayer consisting of poly(ethylene imine) and poly(acrylic acid). Finally, we briefly outline potential future developments in the field of the electrokinetics of polyelectrolyte layers.

Interspecies differences with in vitro and in vivo models of vascular tissue engineering.

In arterial replacement there is a clear clinical need for a functional substitute possessing appropriate haemocompatible properties to be implanted as small diameter artery. Endothelial cell seeding constitutes an appreciated method to improve blood compatibility on the condition that cells firmly adhere to the support. Along this way, an innovative technique based on multilayered polyelectrolyte films (PEM) as cell adhesive substrate was previously validated in vitro and in vivo in a small-animal model. In this study, we extended the work on a larger animal (sheep) to validate furthermore the paradigm of PEM functionalization for vascular substitutes. We tested in vitro: the efficiency of PEM to induce endothelial progenitor differentiation in sheep endothelial cells; the ability of PEM to sustain cell proliferation and allow resistance to shear stress; the fate of PEM-coated de-endothelialized human saphenous veins under flow conditions, a prerequisite step before in vivo experiments. Despite in vitro differences we were encouraged by testing in vivo PEM-coated prosthesis as carotid replacement in sheep, but without success. In order to explain the implantation failure, an in vitro haemocompatibility evaluation was performed that highlighted interspecies differences able to explain, at least in part, the graft failure obtained.