Sequential bond energies of water to sodium glycine cation

Abstract

Absolute bond dissociation energies of water to sodium glycine cations and glycine to hydrated sodium cations are determined experimentally by competitive collision-induced dissociation (CID) of Na +Gly(H 2O) x , x = 1–4, with xenon in a guided ion beam tandem mass spectrometer. The cross sections for CID are analyzed to account for unimolecular decay rates, internal energy of reactant ions, multiple ion–molecule collisions, and competition between reaction channels. Experimental results show that the binding energies of water and glycine to the complexes decrease monotonically with increasing number of water molecules. Ab initio calculations at four different levels show good agreement with the experimental bond energies of water to Na +Gly(H 2O) x , x = 0–3, and glycine to Na +(H 2O), whereas the bond energies of glycine to Na +(H 2O) x , x = 2–4, are systematically higher than the experimental values. These discrepancies may provide some evidence that these Na +Gly(H 2O) x complexes are trapped in excited state conformers. Both experimental and theoretical results indicate that the sodiated glycine complexes are in their nonzwitterionic forms when solvated by up to four water molecules. The primary binding site for Na + changes from chelation at the amino nitrogen and carbonyl oxygen of glycine for x = 0 and 1 to binding at the C terminus of glycine for x = 2–4. The present characterization of the structures upon sequential hydration indicates that the stability of the zwitterionic form of amino acids in solution is a consequence of being able to solvate all charge centers.