Influence of antioxidant structure on local molecular mobility in amorphous sucrose

Abstract

The effect of the antioxidants gallic acid and methyl, propyl, and octyl gallate on the molecular mobility and hydrogen bond network in amorphous sucrose was studied. Solid amorphous sucrose films with and without the addition of antioxidants at a mole ratio of 1:5 (antioxidant/sucrose) were cast from solution onto quartz slides. Local molecular mobility from 0 to 70°C was measured using tryptophan amino acid as a luminescent probe dispersed in the films. Phosphorescence from the tryptophan probe provides spectroscopic characteristics—emission spectrum and lifetime—that are sensitive to changes in molecular mobility induced by the addition of antioxidants. Local molecular mobility detected by tryptophan increased in the following order: sucrose<sucrose–octyl gallate<sucrose–propyl gallate⩽sucrose–methyl gallate⩽sucrose–gallic acid. The antioxidants also modulated the activation energy for matrix motions that quench the tryptophan phosphorescence in a structure-dependent manner. IR measurements as a function of temperature indicated that hydrogen bond strength in these amorphous films followed a rank order (sucrose–methyl gallate>sucrose–gallic acid>sucrose–propyl gallate>sucrose>sucrose–octyl gallate) that was nearly the reverse of that seen in matrix mobility. Analysis of the differential effects of the antioxidants suggests that the presence of the hydroxyl benzoyl head group increased matrix molecular mobility and hydrogen bond strength while the saturated carbon chain decreased mobility and bond strength. The influence of the carboxyl group on matrix properties was comparable to that of the formyloxy group. These results indicate that the addition of specific functional ingredients such as antioxidants may significantly affect the physical properties and consequently functional properties of amorphous edible films in ways that might condition their use. The observed changes are closely related to the chemical structure of the added species.