Layer‐by‐Layer Formation of Polyamine‐Salt Aggregate/Polyelectrolyte Multilayers. Loading and Controlled Release of Probe Molecules from Self‐Assembled Supramolecular Networks

Abstract

The use of soft materials as building blocks in layer‐by‐layer (LbL) assemblies represent a very appealing and useful approach to enhance the loading capacity of thin films. Here, the capacity of positively charged polyamine‐salt aggregates (PSAs) based on ionically crosslinked poly(allylamine hydrochloride) (PAH) with phosphate anions (Pi) is explored to act as building blocks in construction of multilayers by alternated deposition with poly(sodium 4‐styrenesulfonate). Hybrid thin films are successfully prepared by the LbL technique with a highly regular growth and a material deposition rate higher than the traditional full polyelectrolyte LbL. The loading of bromophenol blue (BPB) is evaluated by integration into PSAs followed by LbL deposition and monitored with UV–vis spectroscopy. Finally, the release of the dye molecules is carried out by exposing the film to different aqueous solutions. It is shown that a fully controlled release can be achieved by simply varying the media pH obtaining total BPB release over periods between minutes and months. The data obtained reveal that this new LbL construction strategy using ionically crosslinked PAH/Pi colloids allows to obtain nanoarchitectures with high loading capacity and remarkable properties for controlled release.

Mass and charge transport in highly mesostructured polyelectrolyte/electroactive-surfactant multilayer films

“…These anions represent a benchmark for the study of mass and charge transport in layer-by-layer systems [57,65,85], phenomena that are frequently correlated with the Hofmeister series (and, therefore, with the solvation energy). As is well known, the nature of the anion can have a strong influence on the final properties of charged supramolecular and macromolecular systems [86][87][88].…”

Nanoarchitectonics of metal organic frameworks and PEDOT layer-by-layer electrodes for boosting oxygen reduction reaction

“…[14][15][16] Usually, multilayer composite coatings are obtained by sequential deposition of materials with particular features that allow specific interactions and enable the emergence of functional properties. [17][18][19] In this regard, the construction of multilayer thin-film architectures was already shown to be possible by resorting to hydrogen bonding, electrostatic, and/or van der Waals "soft" interactions. [20][21][22] Aside from the above-mentioned energy-related applications, it can be mentioned also the use of functional multilayer coatings in diverse fields such as drug delivery, biosensing, catalysis, lithography, and electronic signaling and memory.…”

The Effect of Amino–Phosphate Interactions on the Biosensing Performance of Enzymatic Graphene Field-Effect Transistors

“…4,5 Moreover, diatom biosilica is mainly constituted of polyamines of up to 20 repeated units and silaffins, and their interaction with phosphate anions (that serve as ionic cross-linkers) yields aggregates that determines the species-specific patterning of diatom biosilica. 6,7 In addition, polyamine−phosphate interactions have also been used to fabricate abiotic functional structures, such as tunable supramolecular films, 1,8 which can modulate cell adhesion and proliferation. 9 Furthermore, polyamine−phosphate-based systems have also been employed for the construction of drug delivery systems, showing an excellent ability to encapsulate chemotherapeutic agents such as curcumin and doxorubicin.…”

“…The interaction between polyamines and phosphates is a decisive type of noncovalent association that shows relevant implications in a wide range of biological systems. , For instance, nuclear aggregates of biogenic polyamines such as putrescine, spermidine, and spermine and orthophosphate anions (Pi) are present in many replicating cells, and they hierarchically assemble into cyclic structures with high order that are able to protect DNA. , Moreover, diatom biosilica is mainly constituted of polyamines of up to 20 repeated units and silaffins, and their interaction with phosphate anions (that serve as ionic cross-linkers) yields aggregates that determines the species-specific patterning of diatom biosilica. , In addition, polyamine–phosphate interactions have also been used to fabricate abiotic functional structures, such as tunable supramolecular films, , which can modulate cell adhesion and proliferation . Furthermore, polyamine–phosphate-based systems have also been employed for the construction of drug delivery systems, showing an excellent ability to encapsulate chemotherapeutic agents such as curcumin and doxorubicin .…”