Structures of ionic liquids dictate the conversion and selectivity of enzymatic glycerolysis: Theoretical characterization by COSMO‐RS
- 14 June 2007
- journal article
- research article
- Published by Wiley in Biotechnology & Bioengineering
- Vol. 99 (1), 18-29
- https://doi.org/10.1002/bit.21520
Abstract
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. Biotechnol. Bioeng. 2008;99: 18–29.Keywords
This publication has 37 references indexed in Scilit:
- Evaluation of Binary Solvent Mixtures for Efficient Monoacylglycerol Production by Continuous Enzymatic GlycerolysisJournal of Agricultural and Food Chemistry, 2006
- New opportunity for enzymatic modification of fats and oils with industrial potentialsOrganic & Biomolecular Chemistry, 2005
- Prediction of Infinite Dilution Activity Coefficients of Organic Compounds in Ionic Liquids Using COSMO-RSJournal of Chemical & Engineering Data, 2003
- Characterizing Ionic Liquids On the Basis of Multiple Solvation InteractionsJournal of the American Chemical Society, 2002
- The role of hydrogen bonding in controlling the selectivity of Diels–Alder reactions in room-temperature ionic liquidsGreen Chemistry, 2002
- Fast solvent screening via quantum chemistry: COSMO‐RS approachAIChE Journal, 2002
- Molecular states of water in room temperature ionic liquidsElectronic Supplementary Information available. See http://www.rsc.org/suppdata/cp/b1/b106900d/Physical Chemistry Chemical Physics, 2001
- Ionic liquids: Innovative fluids for chemical processingAIChE Journal, 2001
- Solvent engineering applied to lipase‐catalyzed glycerolysis of trioleinJournal of Oil & Fat Industries, 2001
- Lipase-catalyzed syntheses of monoacylglycerolsEnzyme and Microbial Technology, 1995