Binding Energies of Water to Sodiated Valine and Structural Isomers in the Gas Phase: The Effect of Proton Affinity on Zwitterion Stability

Andrew S. Lemoff, Matthew F. Bush, Evan R. Williams

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Abstract

The structures of valine (Val) and methylaminoisobutyric acid (Maiba) bound to a sodium ion, both with and without a water molecule, are investigated using both theory and experiment. Calculations indicate that, without water, sodiated Val forms a charge-solvated structure in which the sodium ion coordinates to the nitrogen and the carbonyl oxygen (NO-coordination), whereas Maiba forms a salt-bridge structure in which the sodium ion coordinates to both carboxylate oxygens (OO-coordination). The addition of a single water molecule does not significantly affect the relative energies or structures of the charge-solvated and salt-bridge forms of either cluster, although in Maiba the mode of sodium ion binding is changed slightly by the water molecule. The preference of Maiba to adopt a zwitterionic form in these complexes is consistent with its higher proton affinity. Experimentally, the rates of water evaporation from clusters of Val·Na+(H2O) and Maiba·Na+(H2O) are measured using blackbody infrared radiative dissociation (BIRD). The dissociation rates from the Val and Maiba complexes are compared to water evaporation rates from model complexes of known structure over a wide range of temperatures. Master equation modeling of the BIRD kinetic data yields a threshold dissociation energy for the loss of water from sodiated valine of 15.9 ± 0.2 kcal/mol and an energy of 15.1 ± 0.3 kcal/mol for the loss of water from sodiated Maiba. The threshold dissociation energy of water for Val·Na+(H2O) is the same as that for the charge-solvated model isomers, while the salt-bridge model complex has the same water threshold dissociation energy as Maiba·Na+(H2O). These results indicate that the threshold dissociation energy for loss of a water molecule from these salt-bridge complexes is ∼1 kcal/mol less than that for loss of water from the charge-solvated complexes.

Original languageEnglish (US)
Pages (from-to)13576-13584
Number of pages9
JournalJournal of the American Chemical Society
Volume125
Issue number44
DOIs
StatePublished - Nov 5 2003

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Valine
Binding energy
Isomers
Protons
Gases
Water
Acids
Salts
Sodium
Ions
Molecules
Evaporation
Oxygen
Infrared radiation
Nitrogen

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Binding Energies of Water to Sodiated Valine and Structural Isomers in the Gas Phase : The Effect of Proton Affinity on Zwitterion Stability. / Lemoff, Andrew S.; Bush, Matthew F.; Williams, Evan R.

In: Journal of the American Chemical Society, Vol. 125, No. 44, 05.11.2003, p. 13576-13584.

Research output: Contribution to journalArticle

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abstract = "The structures of valine (Val) and methylaminoisobutyric acid (Maiba) bound to a sodium ion, both with and without a water molecule, are investigated using both theory and experiment. Calculations indicate that, without water, sodiated Val forms a charge-solvated structure in which the sodium ion coordinates to the nitrogen and the carbonyl oxygen (NO-coordination), whereas Maiba forms a salt-bridge structure in which the sodium ion coordinates to both carboxylate oxygens (OO-coordination). The addition of a single water molecule does not significantly affect the relative energies or structures of the charge-solvated and salt-bridge forms of either cluster, although in Maiba the mode of sodium ion binding is changed slightly by the water molecule. The preference of Maiba to adopt a zwitterionic form in these complexes is consistent with its higher proton affinity. Experimentally, the rates of water evaporation from clusters of Val·Na+(H2O) and Maiba·Na+(H2O) are measured using blackbody infrared radiative dissociation (BIRD). The dissociation rates from the Val and Maiba complexes are compared to water evaporation rates from model complexes of known structure over a wide range of temperatures. Master equation modeling of the BIRD kinetic data yields a threshold dissociation energy for the loss of water from sodiated valine of 15.9 ± 0.2 kcal/mol and an energy of 15.1 ± 0.3 kcal/mol for the loss of water from sodiated Maiba. The threshold dissociation energy of water for Val·Na+(H2O) is the same as that for the charge-solvated model isomers, while the salt-bridge model complex has the same water threshold dissociation energy as Maiba·Na+(H2O). These results indicate that the threshold dissociation energy for loss of a water molecule from these salt-bridge complexes is ∼1 kcal/mol less than that for loss of water from the charge-solvated complexes.",
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AB - The structures of valine (Val) and methylaminoisobutyric acid (Maiba) bound to a sodium ion, both with and without a water molecule, are investigated using both theory and experiment. Calculations indicate that, without water, sodiated Val forms a charge-solvated structure in which the sodium ion coordinates to the nitrogen and the carbonyl oxygen (NO-coordination), whereas Maiba forms a salt-bridge structure in which the sodium ion coordinates to both carboxylate oxygens (OO-coordination). The addition of a single water molecule does not significantly affect the relative energies or structures of the charge-solvated and salt-bridge forms of either cluster, although in Maiba the mode of sodium ion binding is changed slightly by the water molecule. The preference of Maiba to adopt a zwitterionic form in these complexes is consistent with its higher proton affinity. Experimentally, the rates of water evaporation from clusters of Val·Na+(H2O) and Maiba·Na+(H2O) are measured using blackbody infrared radiative dissociation (BIRD). The dissociation rates from the Val and Maiba complexes are compared to water evaporation rates from model complexes of known structure over a wide range of temperatures. Master equation modeling of the BIRD kinetic data yields a threshold dissociation energy for the loss of water from sodiated valine of 15.9 ± 0.2 kcal/mol and an energy of 15.1 ± 0.3 kcal/mol for the loss of water from sodiated Maiba. The threshold dissociation energy of water for Val·Na+(H2O) is the same as that for the charge-solvated model isomers, while the salt-bridge model complex has the same water threshold dissociation energy as Maiba·Na+(H2O). These results indicate that the threshold dissociation energy for loss of a water molecule from these salt-bridge complexes is ∼1 kcal/mol less than that for loss of water from the charge-solvated complexes.

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