Hydration and counterion binding of aqueous acetylcholine chloride and carbamoylcholine chloride

The hydration and Cl^- ion binding of the neurot^†ransmitter acetylcholine (ACh⁺) and its synthetic analogue, carbamoylcholine (CCh⁺), were studied by combining dilute-solution conductivity measurements with dielectric relaxation spectroscopy and statistical mechanics calculations at 1D-RISM and 3D-RISM level. Chloride ion binding was found to be weak but not negligible. From the ∼30 water molecules coordinating ACh and CCh⁺ only ∼1/3 is affected in its rotational dynamics by the cation, with the majority - situated close to the hydrophobic moieties - only retarded by a factor of ∼2.5. At vanishing solute concentration cations and the ∼3-4 H₂O molecules hydrogen bonding to the CO group of the solute exhibit similar rotational dynamics but increasing concentration and temperature markedly dehydrates ACh⁺ and CCh⁺.