Mechanistic insights into the water-catalysed ring-opening reaction of vitamin E by means of double-hybrid density functional theory

Abstract

The potent antioxidant α-tocopherol is known to trap two hydroxyl radicals leading to the formation of the experimentally observed α-tocopherylquinone product. Based on doublehybrid density functional theory calculations, we propose for the first time, a reaction mechanism for the conversion of α-tocopherol to α-tocopherylquinone. We find that a watercatalysed ring-opening reaction plays a key role in this conversion. The water catalysts act as proton shuttles facilitating the proton transfers and reducing the ring strain in the cyclic transition structures. On the basis of the proposed reaction mechanism, we proceed to design an antioxidant with potentially enhanced antioxidant properties.

The mechanism of monochloramine disproportionation under acidic conditions

“…Such approaches have been successful in several earlier studies. [55][56][57] We have constructed models with three water molecules in analogy with models of ref. 55.…”