Typical at glance but interesting when analyzed in detail: A story of Tris hydration

This paper provides results of dielectric relaxation (DR) spectroscopy of aqueous solutions of tris(hydroxymethyl)aminomethane (Tris) covering frequencies of 0.05 ≤ ν/GHz ≤89. The DR spectra can be well fit by a sum of Cole-Cole relaxation, assigned to the solute, and 2 Debye modes already observed for neat water. Analysis of the amplitudes reveals that Tris is hydrated by 7 H₂Os up to its solubility limit. However, the rather high effective solute dipole moment of ≈12 D suggests that H₂O dipoles in contact with Tris should reorient independently from it. Accordingly, an alternative description of the DR spectra with a superposition of 4 Debyerelaxations was attempted. In this model, the slowest mode at ∼4 GHz arises from solute reorientation and that at ∼8 GHz was assigned to dynamically retarded hydration water, whereas relaxations at ∼18 and ∼500 GHz are again those of (rather unperturbed) bulk water. Analysis of the solvent-related modes shows that Tris indeed slows down 7-8 H₂O molecules. However, the solute-solvent interaction strength is rather weak, excluding the rotation of an alleged Tris-(7-8) H₂O cluster as an entity. The now derived effective dipole moment of (6.3 ± 0.5) D for the bare Tris molecule allows speculations on its conformation. With the help of computational methods, we suggest that Tris dissolved in water most likely possesses an intramolecular H-bond between the nitrogen and hydrogen atoms of amino and hydroxyl groups, respectively. In addition, computational results indicate that the seven hydration H₂Os found by DR bind directly to the Tris OH groups.