Acid-base thermochemistry of gaseous oxygen and sulfur substituted amino acids (Ser, Thr, Cys, Met)

Vanessa Riffet (1) , Gilles Frison (1) , Guy Bouchoux (1)

1 DCMR - Laboratoire des mécanismes réactionnels

Acid-base thermochemistry of isolated amino acids containing oxygen or sulfur in their side chain (serine, threonine, cysteine and methionine) have been examined by quantum chemical computations. Density functional theory (DFT) was used, with B3LYP, B97-D and M06-2X functionals using the 6-31+G(d,p) basis set for geometry optimizations and the larger 6-311++G(3df,2p) basis set for energy computations. Composite methods CBS-QB3, G3B3, G4MP2 and G4 were applied to large sets of neutral, protonated and deprotonated conformers. Conformational analysis of these species, based on chemical approach and AMOEBA force field calculations, has been used to identify the lowest energy conformers and to estimate the population of conformers expected to be present at thermal equilibrium at 298 K. It is observed that G4, G4MP2, G3B3, CBS-QB3 composite methods and M06-2X DFT lead to similar conformer energies. Thermochemical parameters have been computed using either the most stable conformers or equilibrium populations of conformers. Comparison of experimental and theoretical proton affinities and Delta(acid)H shows that the G4 method provides the better agreement with deviations of less than 1.5 kJ mol-1. From this point of view, a set of evaluated thermochemical quantities for serine, threonine, cysteine and methionine may be proposed: PA = 912, 919, 903, 938; GB = 878, 886, 870, 899; Delta(acid)H = 1393, 1391, 1396, 1411; Delta(acid)G = 1363, 1362, 1367, 1382 kJ mol-1. This study also confirms that a non-negligible Delta(p)S° is associated with protonation of methionine and that the most acidic hydrogen of cysteine in the gas phase is that of the SH group. In several instances new conformers were identified thus suggesting a reexamination of several IRMPD spectra.

Mots clés: Serine; Threonine; Cysteine; Methionine; DFT calculations; composite methods calculations; proton affinity; gas-phase basicity; protonation entropy; gas phase acidity

Domaines: Chimie théorique et/ou physique

Vanessa Riffet, Gilles Frison, Guy Bouchoux. Acid-base thermochemistry of gaseous oxygen and sulfur substituted amino acids (Ser, Thr, Cys, Met). Physical Chemistry Chemical Physics, 2011, 13, pp.18561-18580. ⟨10.1039/c1cp22206f⟩. ⟨hal-00616361⟩