The kinetics and quantitative and qualitative effects of grape proanthocyanidin (PA) adsorption to grape skin-derived cell wall material (CWM) were investigated in five different temperature-ethanol conditions. Progress curves for each condition were constructed by monitoring the decrease in concentration of PA solutions after exposure to CWM over 720 min. Adsorption isotherms were constructed for each condition, and a Langmuir equation model was applied to each via regression analysis. Compositional changes in the PA solutions after exposure to CWM were determined using phloroglucinolysis and gel permeation chromatography (GPC). A negative correlation between PA adsorption and both the temperature and ethanol concentration was found. Progress curves suggested that both the temperature and ethanol affect the equilibration rate of the adsorption reactions. Additionally, equilibration rates for lower temperature and ethanol concentration conditions were found to be much longer than previously reported, taking up to 720 min. Phloroglucinolysis results showed no discernible correlation between the temperature or ethanol concentration and percent galloylation or percent gallo units of adsorbed compounds. Analyses by phloroglucinolysis and GPC indicate a preferential adsorption of larger molecular weight PAs under all conditions, although no discernible impact on PA composition was detected. Additionally, findings suggest that both the temperature and ethanol concentration impact the percent reduction in molar mass of the PA solution. Data from this study were ultimately utilized to develop a computational model for predicting phenolic extraction during red wine fermentations.
Keywords: adsorption; ethanol; isotherm; kinetic; modeling; proanthocyanidin; temperature; wine.