A study on the progress of mutarotation above and below the Tg and the relationship between constant rates and structural relaxation times.

Comprehensive FTIR studies on the progress of mutarotation in d-fructose mixed with maltitol have been carried out over a wide range of temperatures, both above and below the glass transition temperature T_g. In addition to the analysis of single bands, we have developed a completely new approach considering the full spectral range to follow the overall progress of the reaction. We have found that at the calorimetric T_g, there is a clear change in the temperature dependence of constant rates. The activation barrier for mutarotation changes from around 59 kJ mol⁻¹ (the supercooled state) to around 249 kJ mol⁻¹ (the glassy state). This dramatic variation in the activation barrier is consistent with the change in the mechanism of this specific chemical conversion, as theoretically considered by Wlodarczyk et al. [Phys. Chem. Chem. Phys., 2014, 16, 4694–4698]. Alternatively, it can also be connected to the change in the viscosity of the sample. Additionally, we investigated the relationship between constant rates (k) of mutarotation, structural relaxation times (τ_α), and dc conductivity (σ_dc) above and below the glass transition temperature. It was found that there was a linear correlation between all these quantities; they scale with various exponents changing at T_g. Our results also indicate that a single activation barrier might not be sufficient to describe the mutarotation process. [ABSTRACT FROM AUTHOR]