Structures and hydration enthalpies of cationized glutamine and structural analogues in the gas phase

Andrew S. Lemoff, Matthew F. Bush, Chih Che Wu, Evan R. Williams

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

The structures of lithiated and sodiated glutamine, both with and without a water molecule, are investigated using experiment and theory. Loss of water from these complexes and from lithiated and sodiated complexes of asparagine methyl ester, asparagine ethyl ester, and glutamine methyl ester is probed with blackbody infrared radiative dissociation experiments performed over a wide temperature range. Threshold dissociation energies, Eo, for loss of a water molecule from these complexes are obtained from master equation modeling of these data. The values of Eo are 63 ± 1 and 53 ± 1 kJ/mol for the lithiated and sodiated glutamine complexes, respectively. These values are similar to those for the nonzwitterionic model complexes and are in excellent agreement with calculated values. In contrast, water binding to the zwitterionic form is calculated to be significantly higher. These results indicate that glutamine in these lithiated and sodiated complexes with a water molecule are nonzwitterionic. Complexes with the asparagine side chain have slightly higher Eo values than those with the glutamine side chain, a result consistent with more effective solvation of the metal ion due to the slightly longer side chain of glutamine. Calculations indicate that lithiated and sodiated glutamine are nonzwitterionic, with the metal ion interacting with the amine nitrogen and carbonyl oxygen from the amino acid backbone and the amide oxygen of the side chain. Addition of a water molecule does not affect the lowest-energy structure of lithiated glutamine, whereas, for sodiated glutamine, the lowest-energy zwitterionic and nonzwitterionic structures are essentially isoenergetic.

Original languageEnglish (US)
Pages (from-to)10276-10286
Number of pages11
JournalJournal of the American Chemical Society
Volume127
Issue number29
DOIs
StatePublished - Jul 27 2005

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Glutamine
Hydration
Enthalpy
Gases
Water
Esters
Molecules
Asparagine
Metal ions
Oxygen
Solvation
Metals
Amides
Ions
Amino acids
Amines
Experiments
Nitrogen
Infrared radiation
Amino Acids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Structures and hydration enthalpies of cationized glutamine and structural analogues in the gas phase. / Lemoff, Andrew S.; Bush, Matthew F.; Wu, Chih Che; Williams, Evan R.

In: Journal of the American Chemical Society, Vol. 127, No. 29, 27.07.2005, p. 10276-10286.

Research output: Contribution to journalArticle

Lemoff, Andrew S. ; Bush, Matthew F. ; Wu, Chih Che ; Williams, Evan R. / Structures and hydration enthalpies of cationized glutamine and structural analogues in the gas phase. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 29. pp. 10276-10286.
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