Molecular mobility in a homologous series of amorphous solid glucose oligomers

Abstract

The molecular mobility of amorphous solid biomaterials influences the stability of dried foods and pharmaceuticals, the viability of seeds and spores, and the desiccation-tolerance of organisms during anhydrobiosis. Current understanding of how structure correlates with molecular mobility in the glassy state is inadequate. We used phosphorescence from vanillin dispersed in amorphous films to study the effect of temperature on molecular mobility in the homologous series of oligosaccharides glucose, maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, and maltoheptaose. Phosphorescence emission spectra and intensity decays were collected from −10 to as high as 130°C. Emission peak energy, a measure of the extent of dipolar relaxation around the excited state prior to emission, decreased monotonically with temperature, decreasing more significantly in the glassy state in larger sugars (higher degree of polymerisation). The intensity decays were well fitted with sums of either four (glucose, maltose, maltotriose) or three exponentials (maltotetraose, maltopentaose, maltohexaose, maltoheptaose); fit lifetimes at each temperature varied over nearly two orders of magnitude, suggesting a comparable range in matrix dynamic heterogeneity. The lifetimes decreased monotonically with temperature, while the lifetime amplitudes favoured the long lifetime components at lower and short lifetime components at higher temperatures near Tg. Arrhenius analysis indicated that the rate of non-radiative decay, which reflects coupling of probe vibrations with matrix motions and thus provides an estimate of the matrix molecular mobility, increased with molecular size in the glassy state. Both apparent activation energy and activation entropy increased systematically with temperature in all sugars. These data provide additional evidence that the rate and extent of molecular mobility in glassy state carbohydrates is higher in sugars of greater molecular size (mass) and thus higher glass transition temperature and provides additional insight into the molecular dynamics of the glassy state in carbohydrates.