pH- and Functionalization-Dependent Host-Guest Interactions Between Fluorescein and Various Poly(amidoamine)...

Dendrimers are branched macromolecules that can be functionalized with a large variety of chemical moieties. Dendrimers can therefore be specifically designed to interact with target molecules. Although tailored dendrimers hold promise for targeted drug delivery and wastewater cleanup, these applications require more detailed and systematic studies on how dendrimer-guest interactions depend on environmental conditions. In light of this need, we studied pH-dependent interactions between fluorescein and poly(amidoamine) dendrimers with three different terminal groups. Crucially, both fluorescein and dendrimers have multiple protonation equilibria, which can enable interactions in different pH windows through various possible mechanisms. Such interactions are studied through UV-vis and fluorescence spectroscopies, which reveal a redshift that occurs upon fluorescein-dendrimer binding. The resulting pH-dependent spectra are complex but can be analyzed quantitatively with an open-source mathematical protocol. Consequently, we show that fluorescein binds across four pH units with amine-terminated dendrimers, across two units with hydroxyl-terminated dendrimers and does not interact attractively with carboxyl-terminated dendrimers. These functionalization-dependent host-guest interactions stabilize fluorescein's dianionic form and are predominantly electrostatically driven, with likely auxiliary hydrogen and CH-π bonding. Notably, these auxiliary mechanisms appear too weak to drive dendrimer-fluorescein interactions on their own. Overall, this work yields valuable insights into dendrimer-fluorescein association and provides a readily reproducible framework for studying host-guest interactions.