FREEZE-DRIED BIOMOLECULES - FT-ICR STUDIES OF THE SPECIFIC SOLVATION OF FUNCTIONAL-GROUPS AND CLATHRATE FORMATION OBSERVED BY THE SLOW EVAPORATION OF WATER FROM HYDRATED PEPTIDES AND MODEL COMPOUNDS IN THE GAS-PHASE

Solvent evaporation from extensively hydrated peptides and selected mo del compounds formed by electrospray ionization has been examined usin g an external ion source Fourier transform ion cyclotron resonance (FT -ICR) mass spectrometer. Water evaporation from the clusters, formed a t room temperature by appropriate operation of an electrospray ion sou rce, is initially rapid and results in evaporative cooling of the clus ters to a temperature; around 130-150 K, determined by the balance bet ween evaporative cooling and heating by background blackbody radiation . In this ''freeze-drying'' process, it is observed that the kinetics of solvent evaporation and the cluster size distributions are highly d ependent on the nature of the core ion in the cluster. In agreement wi th earlier studies of the hydrated proton, pure water clusters exhibit special stability characteristic of clathrate formation where, for ex ample, a hydronium ion is encapsulated by a pentagonal dodecahedron of twenty water molecules. Similar clustering of water occurs around pro tonated primary alkylamines where the protonated amine replaces one of the water molecules in the clathrate structures, which encapsulate on e or more neutral water molecules. This observation supports the conje cture that the doubly protonated cyclic decapeptide gramicidin S with 40 water molecules attached,the most significant magic number observed in mass spectra at various delay times, has both protonated ornithine residues solvated by pentagonal dodecahedron clathrate structures. Ot her peptides such as doubly protonated bradykinin do not exhibit any s pecific solvation during the freeze-drying process. Studies of model c ompounds are presented which reveal other interesting aspects of water structure around singly and multiply charged ions with low extents of hydration, including the observation of neutral clathrates attached t o a ''spectator'' ion.