Protein-based polyelectrolyte multilayers.

The immobilization of proteins to impart specific functions to surfaces is topical for chemical engineering, healthcare and diagnosis. Layer-by-Layer (LbL) self-assembly is one of the most used method to immobilize macromolecules on surfaces. It consists in the alternate adsorption of oppositely charged species, resulting in the formation of a multilayer. This method in principle allows any charged object to be immobilized on any surface, from aqueous solutions. However, when it comes to proteins, the promises of versatility, simplicity and universality that the LbL approach holds are unmet due to the heterogeneity of protein properties. In this review, the literature is analyzed to make a generic approach emerge, with a view to facilitate the LbL assembly of proteins with polyelectrolytes (PEs). In particular, this review aims at guiding the choice of the PE and the building conditions that lead to the successful growth of protein-based multilayered self-assemblies.

Biofunctionalized and self-supported polypyrrole frameworks as nanostructured ECM-like biointerfaces.

Hybrid nanobiointerfaces were designed as an original contribution to the challenge of synthesizing nanostructured biomaterials integrating a set of cell fate-determining cues, originally provided to cells by the extracellular matrix (ECM). The produced biointerfaces consist of a stiff framework of intersected polypyrrole (PPy) nanotubes supporting a soft multilayer composed of ECM-derived biomacromolecules: collagen (Col) and hyaluronic acid (HA). PPy frameworks with highly tunable characteristics were synthesized through chemical oxidative polymerization of pyrrole monomers, templated within track-etched polycarbonate (PC) membranes featuring a network of intersected nanopores. PPy interfaces with a porosity of 80%, composed of nanotubes with an average diameter ranging from 40 to 300 nm, intersecting at an angle of 90°, were shown to be self-supported. These rigid PPy nanostructured interfaces were functionalized with a self-assembling (HA/Col) multilayer deposited via a layer-by-layer process. Biofunctionalized and unmodified PPy frameworks were both shown to promote sustained cell adhesion, therefore demonstrating the cytocompatibility of the engineered matrices. Such nanobiointerfaces, combining a mechanically-stable framework of tunable dimensions with a soft biopolymeric multilayer of highly versatile nature, pave the way towards cell-instructive biomaterials able to gather a wide range of cues guiding cell behavior. The developed self-supported structures could be used as a coating or as membranes bridging different tissues.

Universal Method to Transfer Membrane-Templated Nano-Objects to Aqueous Solutions.

A wide range of nano-objects are synthesized by combining template synthesis, using polycarbonate membrane as template, with different material deposition methods. The resulting nanostructures varied from robust inorganic gold nanowires grown by electrodeposition to rigid polypyrrole nanotubes synthesized by chemical polymerization and softer nanotubes made of different combinations of synthetic and natural polyelectrolytes fabricated by layer-by-layer (LbL) assembly. The morphology of these various nano-objects is characterized prior to and after their immersion in water, revealing that the rigidity degree of LbL nanotubes strongly decreases after being in contact with water, leading to highly swollen and flexible nanotubes in aqueous solution that tend to stick to any surface and are very difficult to collect and disperse quantitatively in aqueous solution. Different processes to collect these nano-objects and disperse them in aqueous medium for further analysis and application were then studied. Among them, a method based on simple filtration of nanotubes in the presence of a powdered dextran adjuvant leads to the quantitative collection and dispersion in water of all types of tested cylindrical nano-objects. This universal method to efficiently collect membrane templated nano-objects paves the way to further characterization of a large variety of nanotubes in aqueous solution and to their potential use as cargo nanocarriers or as nanoreactors.