General acid/base catalysis of sugar anomerization

Abstract

Based on theoretical and mechanistical considerations, an equation is presented that describes the observed rate of a pH sensitive reaction. In contrast to the commonly used catalytic catenary, the new approach enables the calculation of non-biased thermodynamic activation parameters. Applying this model, the general acid/base catalysis of the ring opening of β-d-fructopyranose was analyzed polarimetrically. Thereby, it could be shown that acids (bases) catalyze the ring opening of anionic (cationic) sugar species. Since anomerization rate constants correlate with the rate of sugar degradation, catalysts of anomerization will increase the sugar's reactivity as well. The most effective catalysts of the ring opening of β-d-fructopyranose in the food relevant pH milieu are weak acids and their conjugated bases. Consequently, the enhanced reactivity of reducing sugars in the presence of amino acids is not solely due to classical Maillard reaction but primarily due to carboxylic acid catalysis of degradation reactions.

Keywords: Acid/base catalysis; Anomerization; Equilibration; Maillard reaction; NMR spectroscopy; Polarimetry; Ring opening; d–Fructose.