Poly(allylamine)-tripolyphosphate Ionic Assemblies as Nanocarriers: Friend or Foe?

Designing effective drug nanocarriers that are easy to synthesize, robust, and nontoxic is a significant challenge in nanomedicine. Polyamine-multivalent molecule nanocomplexes are promising drug carriers due to their simple and all-aqueous manufacturing process. However, these systems can present issues of colloidal instability over time and cellular toxicity due to the cationic polymer. In this study, we finely modulate the formation parameters of poly(allylamine-tripolyphosphate) complexes to jointly optimize the robustness and safety. Polyallylamine was ionically assembled with tripolyphosphate anions to form liquid-like nanocomplexes with a size of around 200 nm and a zeta potential of -30 mV. We found that nanocomplexes exhibit tremendous long-term stability (9 months of storage) in colloidal dispersion and that they are suitable as protein-loading agents. Moreover, the formation of nanocomplexes induced by tripolyphosphate anions produces a switch-off in the toxicity of the system by altering the overall charge from positive to negative. In addition, we demonstrate that nanocomplexes can be internalized by bone-marrow-derived macrophage cells. Altogether, these nanocomplexes have attractive and promising properties as delivery nanoplatforms for potential therapies based on the immune system activation.

Electrochemically addressed FET-like nanofluidic channels with dynamic ion-transport regimes.

Nanofluidic channels in which the ionic transport can be modulated by the application of an external voltage to the nanochannel walls have been described as nanofluidic field effect transistors (nFETs) because of their analogy with electrolyte-gated field effect transistors. The creation of nFETs is attracting increasing attention due to the possibility of controlling ion transport by using an external voltage as a non-invasive stimulus. In this work, we show that it is possible to extend the actuation range of nFETs by using the supporting electrolyte as a "chemical effector". For this aim, a gold-coated poly(ethylene terephthalate) (PET) membrane was modified with electroactive poly-o-aminophenol. By exploiting the interaction between the electroactive poly-o-aminophenol and the ions in the electrolyte solution, the magnitude and surface charge of the nanochannels were fine-tuned. In this way, by setting the electrolyte nature it has been possible to set different ion transport regimes, i.e.: cation-selective or anion-selective ion transport, whereas the rectification efficiency of the ionic transport was controlled by the gate voltage applied to the electroactive polymer layer. Remarkably, under both regimes, the platform displays a reversible and rapid response. We believe that this strategy to preset the actuation range of nFETs by using the supporting electrolyte as a chemical effector can be extended to other devices, thus offering new opportunities for the development of stimulus-responsive solid-state nanochannels.