Diffusion coefficients are utilised to provide a realistic approach in the quantification of mass transport phenomena, which are important for the delivery of bioactivity from high-solid biopolymer systems. Following this mechanistic consideration, we employ spray drying to produce microcapsules of waxy maize starch that suspend homogeneously tocopheryl acetate. An array of physicochemical techniques including dynamic oscillation in-shear or compression mode, microDSC, WAXD, FTIR, scanning electron or optical microscopy, and UV-vis assays were utilised to relate structural properties of the macromolecular network to diffusivity of the bioactive compound. A modified version of the free-volume theory designed to address molecular diffusion was evaluated over a wide temperature range. Predictive capabilities were facilitated by proposing a mathematical relationship between diffusion coefficient of tocopheryl acetate and fractional free volume of waxy maize starch. Moreover, the theoretical approach is able to accurately describe the extent of cooperativity in the vitamin-biopolymer interaction that determines transport kinetics.
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