The concept of regulating the preference of a reversible multi-step reaction by adjusting the substituents of ionic liquids (ILs) has been successfully exemplified with a group of tetraammonium-based ionic liquids as medium for the enzymatic glycerolysis. Simultaneous existence of long chain hydrophobic substituents and hydrophilic ethoxyl or hydroxyl moieties is found, respectively, to be essential for triglycerides (TG) dissolving and equilibrium shifting. The reactions in the ILs with cations consisting of long chain and free hydroxyl groups gave markedly higher conversion of TG and better preference to monoglyceride formation. Interestingly the predicted results from COSMO-RS (a quantum chemical model programme) achieved a good agreement with the experimental data, mapping out the specific solvation from the ILs as well as demonstrating the interaction between ILs, substrates and products being the intrinsic causes that govern reaction evolution and direct equilibrium shifting.
Lipase-catalyzed glycerolysis of triolein has been examined using a group of tetraammonium-based ionic liquids (ILs) as media, specifically with functional groups in cation part. The results demonstrated that the reaction evolution and profile specificity of respective IL system could be quantitatively associated with the structural characteristics of the IL by means of quantum chemical and COSMO-RS calculation. Misfit interaction, Van der Waals interaction and chemical potential, etc. derived from COSMO-RS calculation are shown to be effective measures to delineate multiple interactions of ILs and then can be used to understand the effects of ILs on reactions. The hydrophobic substituents in the cation are found to contribute to the increase of triolein solubility and enhancement of initial reaction rate; while strong polar anion and polyethoxyl and free hydroxyl groups in the cation part dictate improved product selectivity through reducing activity coefficients of monoglycerides. Integration of these structures into the same molecule constitutes a promising group of ILs that could produce over 90% monoglyceride with almost 100% triglyceride conversion, as well as bulky productivity, of particular potential for industrial applications. Overall, this work has presented a first attempt to characterize the IL structure-dependency of reaction specificity by associating structural variations of ILs with thermodynamic property changes of resided compounds and subsequent effects on reaction specificity. This might be of general value to help to understand the multiple solvation interaction among IL reaction systems at molecular level and promote the application of IL-mediated reactions to practical interests.
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