Density functional theory (B3LYP//6-311+G*) calculations, including Poisson-Boltzmann implicit solvent and free energy corrections, are applied to study the hydration of methylglyoxal and the subsequent formation of dimeric species in solution. Our calculations show that, unlike glyoxal, fully hydrated species are not thermodynamically favored over their less hydrated counterparts, nor are dioxolane ring species the thermodynamic sink, which is in agreement with experimental data. Instead, we find that aldol condensations are the most favored oligomerization reactions for methylglyoxal. These results differ from those of glyoxal, which, lacking the methyl group, cannot access the enol structure leading to aldol condensation. For methylglyoxal, the product from nucleophilic attack at the aldehyde rather than the ketone was favored. Our results help explain some of the observed differences between methylglyoxal and glyoxal, in particular the different array of oligomers formed.

Density functional theory calculations, including Poisson-Boltzmann implicit solvent and free energy corrections, are applied to study the mechanism of experimentally observed imidazole formation from the reaction of glyoxal and methylamine in solution. Our calculations suggest that a diimine species is an important intermediate in the reaction. Under acidic conditions, we find that the diimine acts as a nucleophile in attacking the carbonyl group of either formaldehyde or glyoxal to first generate an acyclic enol intermediate, which then goes on to close the ring and form imidazoles. Our results confirm that formaldehyde and, by extension, other small aldehydes are likely to be incorporated into imidazole ions in the presence of glyoxal and primary amines in clouds and aqueous aerosol. This is a new mechanism of aerosol formation by formaldehyde, the most abundant aldehyde in the atmosphere. The amount of aerosol formed will depend on the amounts of glyoxal and amines present.