Molecular mobility modulates the chemical and physical stability of amorphous biomaterials. This study used steady-state and time-resolved phosphorescence of erythrosin B to monitor mobility in thin films of amorphous solid sucrose as a function of temperature. The phosphorescence intensity (lifetime), emission energy, and red-edge excitation effect were all sensitive to localized molecular mobility on the microsecond timescale in the glass and to more global modes of mobility activated at the glass transition. Blue shifts in the emission spectrum with time after excitation and systematic variations in the phosphorescence lifetime with wavelength indicated that emission originates from multiple sites ranging from short lifetime species with red-shifted emission spectrum to long lifetime species with blue-shifted emission spectrum; the activation energy for nonradiative decay of the triplet state was considerably larger for the blue-emitting species in both the glass and the melt. This study illustrates that phosphorescence from erythrosin B is sensitive both to local dipolar relaxations in the glass as well as more global relaxations in the sucrose melt and provides evidence of the value of phosphorescence as a probe of dynamic site heterogeneity as well as overall molecular mobility in amorphous biomaterials.

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Luminescence from the triplet probe erythrosin B (tetra-iodo fluorescein, Ery B) provides spectroscopic characteristics such as lifetime and emission energy that are sensitive to molecular mobility of the local environment in amorphous solids. This study investigated how variations in the local concentration of Ery B free acid as well as the presence of the dispersing solvent affect the spectroscopic measurements of solid matrix properties (the free acid of Ery B is poorly soluble in water and thus must be introduced via an organic solvent). The emission energy of Ery B from 5 to 100 degrees C in thin films of amorphous sucrose at various probe and solvent (N,N-dimethyl formamide, DMF) concentrations was determined using excitation at 500 nm and emission over the range 520-750 nm. The emission lifetime was determined over the same temperature range using a stretched exponential analysis of intensity decays collected using excitation at 530 nm and emission at 680 nm. Variations in the probe/sucrose mole ratio (concentration) over the range from 0.5 to 10 x 10(-4) and 10-fold variations in the amount of DMF used to disperse the probe did not affect the emission energy, the shape of the emission spectra, or the measured lifetimes of Ery B in amorphous sucrose. These results thus indicate that erythrosin B introduced into amorphous solids can provide a robust measure of the intrinsic mobility of the solid matrix that is relatively insensitive to final probe concentration or presence of residual solvent.