Highly-organized stacked multilayers via layer-by-layer assembly of lipid-like surfactants and polyelectrolytes. Stratified supramolecular structures for (bio)electrochemical nanoarchitectonics

Abstract

Supramolecular self-assembly is of paramount importance for the development of novel functional materials with molecular-level feature control. In particular, the interest in creating well-defined stratified multilayers through simple methods using readily available building blocks is motivated by a multitude of research activities in the field of "nanoarchitectonics" as well as evolving technological applications. Herein, we report on the facile preparation and application of highly organized stacked multilayers via layer-by-layer assembly of lipid-like surfactants and polyelectrolytes. Polyelectrolyte multilayers with high degree of stratification of the internal structure were constructed through consecutive assembly of polyallylamine and dodecyl phosphate, a lipid-like surfactant that act as a structure-directing agent. We show that multilayers form well-defined lamellar hydrophilic/hydrophobic domains oriented parallel to the substrate. More important, X-ray reflectivity characterization conclusively revealed the presence of Bragg peaks up to fourth order, evidencing the highly stratified structure of the multilayer. Additionally, hydrophobic lamellar domains were used as hosts for ferrocene in order to create an electrochemically active film displaying spatially-addressed redox units. Stacked multilayers were then assembled integrating redox-tagged polyallylamine and glucose oxidase into the stratified hydrophilic domains. Bioelectrocatalysis and "redox wiring" in the presence of glucose was demonstrated to occur inside the stratified multilayer.

One-step procedure for the preparation of functional polysaccharide/fatty acid multilayered coatings

“…To achieve this, intense work has been conducted on the preparation of composite coatings where polymeric materials are combined with low-molecular-weight block copolymer or surfactant assemblies, i.e., micelles, vesicles, or bilayers [15][16][17][18][19][20] . The stratified structure of alternating lipid or surfactant and polyelectrolyte layers has shown highly promising results in the fields of bio-catalysis and bio-sensing and is generally prepared by sequential adsorption of the different components [21][22][23] . However, for the incorporation of micelles, intact vesicles, or amphiphilic bilayers into multilayered films, additional steps aimed at stabilizing intermediate structures are required 16,17,19 .…”

Molecular Design of Solid‐State Nanopores: Fundamental Concepts and Applications

“…In recent years, the modification of solid‐state nanopores via polyelectrolyte assembly/adsorption has gained increasing interest . The LbL assembly of polyelectrolytes represents a very simple and versatile chemical method to create functional thin films with nanoscale precision . This functionalization method is based on the alternate deposition of polyanions and polycations on solid surfaces leading to the formation of polyelectrolyte multilayers .…”

Electrochemical-QCMD Control over S-Layer (SbpA) Recrystallization with Fe2+ as Specific Ion for Self-Assembly Induction

“…Such behaviour confirms the great isolating capability of these films in spite of their nanometric thickness. Obviously, the presence of multiple pores all over the structure (at the central position in between the four subunits forming the square) enables a higher transfer of sufficiently small ions than, for instance, a homogeneous polymer film [31,32]. A more detailed observation of the plots, as offered by the insets on top, allows a clear distinction between films built in the presence of different counterions.…”