Interactions in plasticizer mixtures used for sugar replacement.

In our quest for novel ingredients to be used in sugar replacement strategies, we have investigated the thermodynamics of polycarboxylic acids, such as citric acid. We have demonstrated the applicability of the Flory-Huggins (FH) theory to describe the thermodynamics of polycarboxylic acids solutions. Moreover, for citric acid we can describe the complete phase diagram with the theory. It shows that polycarboxylic acids have similar plasticizing and hygroscopic properties as sugars and polyols. Regarding mixtures of polycarboxylic acids and carbohydrates, the FH theory is able to describe a) the water activity of the mixtures, b) the solubility of ternary mixtures of acids and sugars, c) the lowering of the deliquescence point for binary mixtures of crystals, and d) the melting point depression in eutectic mixtures. Unexpectingly, our investigations show there is a strong non-zero FH interaction parameter between carboxylic acids and carbohydrates. In our prior sugar replacement strategy we have assumed zero interactions between plasticizers. Here, we will readdress this assumption. Carefull investigations of solid-liquid equilibrium of eutectic mixtures involving polycarboxylic acids and/or carbohydrates, shows nearly zero interaction in eutectic mixtures consisting only of two carbohydrates or two polycarboxylic acids. We now hold the hypothesis that there is strong non-zero interaction if the mixture contains plasticizers strongly differing in the amount of hydrogen bonding groups. This strong interaction explains why these mixtures, like polycarboxylic acids and carbohydrates, are excellent candidates as deep eutectic solvents. Furthermore, we conclude that polycarboxylic acids are useful additions to the toolbox of sugar replacers, albeit that there are some limitations to their amounts used.