Four generations of water-soluble dendrimers with 9 to 243 benzoate tethers: synthesis and dendritic effects on their ion pairing with acetylcholine, benzyltriethylammonium, and dopamine in water

Water-soluble benzoate-terminated dendrimers of four generations (from G0 with 9 branches to G3 with 243 branches) were synthesized and fully characterized. They form water-soluble assemblies by ion-pairing interactions with three cations of medicinal interest (acetylcoline, benzyltriethylammonium, and dopamine), which were characterized and investigated by 1H NMR spectroscopy, whereas such interactions do not provoke any significant shift of 1H NMR signals with the monomeric benzoate anion. The calculated association constants confirm that the dendritic carboxylate termini reversibly form ion pairs and aggregates. Diffusion coefficients and hydrodynamic diameters of the dendrimers, as well as changes thereof on interaction with the cations, were evaluated by DOSY experiments. The lack of increase of dendrimer size on addition of the cations and the upfield shifts of the 1H NMR signals of the cation indicate encapsulation within the hydrophobic dendrimer interiors together with probable backfolding of the benzoate termini.