Dynamic site heterogeneity in amorphous maltose and maltitol from spectral heterogeneity in erythrosin B...

We have used phosphorescence from erythrosin B (tetraiodofluorescein) dispersed in thin films of either maltose or maltitol to investigate the physical properties of these amorphous pure sugar matrixes. Intensity decays collected as a function of emission wavelength over the range from 640 to 720 nm were analyzed using a stretched exponential kinetic model in which the lifetime (tau) and the stretching exponent (beta) were the physically relevant parameters. The lifetimes varied systematically with emission wavelength in both matrixes. Analysis of the temperature dependence of the lifetime at each wavelength provided an estimate of the activation energy for nonradiative quenching of the triplet state; the activation energy also varied with emission wavelength. In addition, time-resolved emission spectra exhibited a blue shift with time following excitation. These data support a photophysical model in which probes are distributed among sites that vary in terms of overall molecular mobility and in which sites with lower rates of dipolar relaxation also have lower rates of collisional quenching of the erythrosin triplet state. The amorphous matrix of both maltose and maltitol in both the glass and the melt state is thus characterized by dynamic site heterogeneity in which different sites vary in terms of their overall molecular mobility.