Hydration of Guanidinium Ions: An Experimental Search for Like-Charged Ion Pairs

Guanidinium ions (GdmH⁺) are reported to form stable complexes (GdmH⁺/GdmH⁺) in aqueous solution despite strong repulsive interactions between the like-charged centers. These complexes are thought to play important roles in protein folding, membrane penetration, and formation of protein dimers. Although GdmH⁺ ions are weakly hydrated, semiempirical calculations provide evidence that these like-charged complexes are stabilized by water molecules, which serve important structural and energetic roles. Specifically, water molecules bridge between the GdmH⁺ ions of GdmH⁺/GdmH⁺ complexes as well as complexes involving the guanidinium side chains of arginine. Potential biological significances of like-charged complexes have been largely confirmed by ab initio molecular dynamics simulations and indirect experimental evidence. We report cryo-ion mobility-mass spectrometry results for the GdmH⁺/GdmH⁺ ion pair confined in a nanodroplet- the first direct experimental observation of this like-charged complex. A second like-charged complex, described as a water-mediated complex involving GdmH⁺ and H₃O⁺, was also observed.