Combined use of thermomechanics and UV spectroscopy to rationalize the kinetics of bioactive compound (caffeine) mobility in a high solids matrix.
An investigation of the diffusional mobility of a bioactive compound (caffeine) within a carbohydrate matrix (glucose syrup) at a glassy consistency is reported. The experimental temperature range was from 30 to - 70 degrees C, and the techniques of modulated differential scanning calorimetry, small-deformation dynamic oscillation on shear, and UV spectrometry were employed. It is not a straightforward matter to identify the relaxation dynamics of such a glassy matrix. This makes suggestions of the relationship between the structural properties of the matrix and the diffusional mobility of bioactive compounds reported earlier in the literature rather tenuous. To address this issue, we recorded mechanical spectra over the aforementioned temperature range and utilized the combined framework of the Williams, Landel, and Ferry (WLF) equation with the time-temperature superposition principle to rationalize results. The protocol produced a fundamental definition of the glass transition temperature and free volume parameters of the glucose syrup sample within the glass transition region. Results were related to the kinetic rates of caffeine diffusion derived by UV spectroscopy leading to the conclusion that the diffusional mobility of the chemical substance is independent of the carbohydrate matrix. This conclusion was further supported by the high level of fractional free volume of caffeine, which is congruent with the predictions of the reaction rate theory (modified Arrhenius equation), as compared to the collapsing levels of free volume in the glucose-syrup matrix that make appropriate WLF considerations.
Kasapis
Stefan
S
School of Applied Sciences, RMIT University, City Campus, Victoria, Australia. stefan.kasapis@rmit.edu.au.
Shrinivas
Preeti
P
D002110:Caffeine / Q000737:chemistry*; D004058:Diffusion; D005947:Glucose / Q000737:chemistry*; D007700:Kinetics; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics
D002110:Caffeine; D005947:Glucose