Structures of cationized proline analogues: Evidence for the zwitterionic form

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

Research output: Contribution to journalArticlepeer-review

76 Scopus citations


The structures of lithiated and sodiated α-methyl-proline (α-Me-Pro) and structural isomers, both with and without a water molecule, are investigated using blackbody infrared radiative dissociation (BIRD) and density functional theory. From the BIRD kinetic data measured as a function of temperature, combined with master equation modeling of these data, threshold dissociation energies for the loss of a water molecule from these clusters are obtained. These energies are 77.5 ± 0.5 and 53 ± 1 kJ/mol for lithiated and sodiated α-Me-Pro, respectively. For the nonzwitterionic isomer, proline methyl ester, these values are 3.0-4.5 kJ/mol higher. These results provide compelling experimental evidence that α-Me-Pro is zwitterionic in these clusters. Theory at the temperature corrected B3LYP/6-311++G**//B3LYP/6-31++G** level indicates that the salt-bridge or zwitterionic forms of lithiated and sodiated α-Me-Pro are between 17 and 23 kJ/mol lower in energy than the nonzwitterionic or charge-solvated forms and that attachment of a single water molecule does not significantly change the structure or the relative energies of these clusters. The proton affinity of proline is 8 kJ/mol higher than that of α-Me-Pro, indicating that lithiated and sodiated singly hydrated proline should also be zwitterionic.

Original languageEnglish (US)
Pages (from-to)1903-1910
Number of pages8
JournalJournal of Physical Chemistry A
Issue number9
StatePublished - Mar 10 2005

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


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