Short Communication

Journal of the American Society for Mass Spectrometry

, Volume 8, Issue 5, pp 565-568

First online:

Hydration of gas-phase gramicidin S (M + 2H)2+ ions formed by electrospray: The transition from solution to gas-phase structure

  • Sandra E. Rodriguez-CruzAffiliated withDepartment of Chemistry, University of California
  • , John S. KlassenAffiliated withDepartment of Chemistry, University of California
  • , Evan R. WilliamsAffiliated withDepartment of Chemistry, University of California

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Abstract

The hydration of doubly protonated gas-phase ions of gramicidin S formed by electrospray ionization was investigated. Under “gentle” electrospray conditions, a near Gaussian distribution of (M + 2H + nH2O)2+ ions with n up to 50 can be readily formed. These extensively hydrated gas-phase ions should have structures similar to those in solution. For intermediate extents of hydration, the “naked” or unsolvated ion is present in unusually high abundance. This is attributed to a competition between solvation of the charges by water vs intramolecular self-solvation via hydrogen bonding. In addition, “magic” numbers of attached water molecules are observed for n = 8, 11, and 14. These magic numbers are attributed to favorable arrangements of water molecules surrounding the charge and surface of the peptide in the gas phase. These results are indicative of a gentle stepwise transformation from the solution-phase structure of the ion to the preferred gas-phase structure as solvent evaporates from the hydrated ions.