Electrochemical behaviour of poly(amidoamine) dendrimers at micropipette-based liquid/liquid micro-interfaces

Dendrimers are macromolecules with well-defined three-dimensional structures, sizes and surface charges. In this work, four generations of poly(amidoamine) (PAMAM) dendrimers were investigated at the micro-interface between two immiscible electrolyte solutions (μITIES) to understand their electrochemical responses as simple models of ionised macromolecules. Cyclic voltammetry (CV) across a range of aqueous phase pH revealed that all four generations (G0-G3) presented diffusion-controlled ion-transfer from aqueous to organic phase, while the reverse transfers from organic to aqueous phase varied with both pH and the dendrimer generation. The larger dendrimers (G2 and G3) show an adsorption behaviour at pH ≤ 3.5, but show a diffusional response at pH ≥ 6. On the other hand, the smaller dendrimers (G0 and G1) always show a diffusional response and are not impacted by the pH. This indicates that more highly charged dendrimers condense at the interface. The reverse scan of CVs showed that an increased applied potential was required to remove (desorb) these polycations from the interfaces in comparison to smaller, less charged species. Diffusion coefficients (D) were estimated, showing a decrease with increasing generation. Limits of detection for these dendrimers by CV at the μITIES were 0.4, 0.2, 0.7 and 0.5 μM for G0 to G3, respectively, while differential pulse voltammetry lowered the LODs (0.07, 0.05, 0.09 and 0.08 μM, respectively). These study shows that the μITIES provides a simple way to detect and evaluate the electrochemical behaviour of ionised macromolecules, providing a simple illustration of detection mechanism with diffusion or adsorption processes.