Collision dynamics of protonated N-acetylmethionine with singlet molecular oxygen (a(1)Δg): the influence of the amide bond and ruling out the complex-mediated mechanism at low energies.

It has been proposed (J. Phys. Chem. B 2011, 115, 2671) that the ammonium group is involved in the gas-phase reaction of protonated methionine (MetH(+)) with singlet oxygen (1)O2, yielding hydrogen peroxide and a dehydro compound of MetH(+) where the -NH3(+) transforms into cyclic -NH2-. For the work reported, the gas-phase reaction of protonated N-acetylmethionine (Ac-MetH(+)) with (1)O2 was examined, including the measurements of reaction products and cross sections over a center-of-mass collision energy (Ecol) range from 0.05 to 1.0 eV using a guided-ion-beam apparatus. The aim is to probe how the acetylation of the ammonium group affects the oxidation chemistry of the ensuing Ac-MetH(+). Properties of intermediates, transition states, and products along the reaction coordinate were explored using density functional theory calculations and Rice-Ramsperger-Kassel-Marcus (RRKM) modeling. Direct dynamics trajectory simulations were carried out at Ecol of 0.05 and 0.1 eV using the B3LYP/4-31G(d) level of theory. In contrast to the highly efficient reaction of MetH(+) + (1)O2, the reaction of Ac-MetH(+) + (1)O2 is extremely inefficient, despite there being exoergic pathways. Two product channels were observed, corresponding to transfer of two H atoms from Ac-MetH(+) to (1)O2 (H2T), and methyl elimination (ME) from a sulfone intermediate complex. Both channels are inhibited by collision energies, becoming negligible at Ecol > 0.2 eV. Analysis of RRKM and trajectory results suggests that a complex-mediated mechanism might be involved at very low Ecol, but direct, nonreactive collisions prevail over the entire Ecol range and physical quenching of (1)O2 occurs during the early stage of collisions.