jp071168a_si_001.pdf (218.92 kB)
Radical-Cationic Gaseous Amino Acids: A Theoretical Study
journal contribution
posted on 2007-08-16, 00:00 authored by Kailee N. Sutherland, Philippe C. Mineau, Galina OrlovaThree major forms of gaseous radical-cationic amino acids (RCAAs), keto (COOH), enolic (C(OH)OH), and
zwitterionic (COO-), as well as their tautomers, are examined for aliphatic Ala•+, Pro•+, and Ser•+, sulfur-containing Cys•+, aromatic Trp•+, Tyr•+, and Phe•+, and basic His•+. The hybrid B3LYP exchange-correlation
functional with various basis sets along with the highly correlated CCSD(T) method is used. For all RCAAs
considered, the main stabilizing factor is spin delocalization; for His•+, protonation of the basic side chain is
equally important. Minor stabilizing factors are hydrogen bonding and 3e−2c interactions. An efficient spin
delocalization along the N−Cα−C(O−)O moiety occurs upon H-transfer from Cα to the carboxylic group to
yield the captodative enolic form, which is the lowest-energy isomer for Ala•+, Pro•+, Ser•+, Cys•+, Tyr•+,
and Phe•+. This H-transfer occurs in a single step as a 1,3-shift through the σ-system. For His•+, the lowest-energy isomer is formed upon H-transfer from Cα to the basic side chain, which results in a keto form, with
spin delocalized along the NCαCO fragment. Trp•+ is the only RCAA that favors spin delocalization
over an aromatic system given the low ionization energy of indole. The lowest-energy isomer of Trp•+ is a
keto form, with no H-transfer.