Functional dependency of structures of ionic liquids: do substituents govern the selectivity of enzymatic glycerolysis?
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.
Guo
Zheng
Z
BioCentrum-DTU, Technical University of Denmark, Building 221, DK-2800, Lyngby, Denmark.
Chen
Biqiang
B
López Murillo
Rafael
R
Tan
Tianwei
T
Xu
Xuebing
X
D005990:Glycerol / Q000737:chemistry* / Q000378:metabolism; D006868:Hydrolysis; D007477:Ions; D008049:Lipase / Q000737:chemistry* / Q000378:metabolism; D015394:Molecular Structure; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics
D007477:Ions; D000644:Quaternary Ammonium Compounds; D012997:Solvents; D008049:Lipase; D005990:Glycerol