Are Nanoscale Ion Aggregates Present in Aqueous Solutions of Guanidinium Salts?

Abstract

A detailed investigation using broadband dielectric relaxation spectroscopy (DRS) has been made of the aqueous solutions of guanidinium chloride and carbonate, GdmCl(aq) and Gdm₂CO₃(aq), at 25 °C. The spectra indicate that Gdm(+) ions, C(NH₂)₃(+), do not bind strongly to water nor are they hydrophobically hydrated; rather they appear to have a most unusual ability to dissolve in water without altering its dynamics. Although DRS is particularly sensitive to the presence of ion pairs, only weak ion pairing was detected in Gdm₂CO₃(aq) solutions and none at all in GdmCl(aq). Surprisingly, no evidence was found for the existence of the higher order homo- and heteroionic nanoscale aggregates that have been identified in recent years by Mason and co-workers using molecular dynamics simulations and neutron diffraction. Possible reasons for this discrepancy are discussed. The present DR spectra and other solution properties of GdmCl(aq) and Gdm₂CO₃(aq), such as apparent molar volumes and electrical conductivities, are shown to have strong similarities to those of the corresponding Na+ salts. However, such solutions also differ remarkably from their Na(+) analogues (and all other simple electrolytes in aqueous solution) in that their average water relaxation times correlate strongly with their bulk viscosities. The biological implications of the present results are briefly discussed.