Water dynamics in the hydration shell of hyper-branched poly-ethylenimine

We performed THz and GHz dielectric relaxation spectroscopy to investigate the reorientational dynamics of water molecules in the hydration shell of amphiphilic hyper-branched poly-ethylenimine (HPEI). Four Debye equations were employed to describe four types of water in the hydration shell, including bulk-like water, under-coordinated water, slow water (water molecules hydrating the hydrophobic groups and water molecules accepting hydrogen bonds from the NH₂ groups) and super slow water (water molecules donating hydrogen bonds to and accepting hydrogen bonds from NH groups). The time scales of undercoordinated and bulk-like water show a slight decline from 0.4 to 0.1 ps and from 8 to 2 ps, respectively. Because of hydrophilic amino groups, HPEI molecules exhibit a strong retardation effect, where the time scales of slow and super slow water increase with concentration from 17 to 39.9 ps and from 88 to 225 ps, respectively.