Kinetics and Mechanism of Solvent Influence on the Lipase-Catalyzed 1,3-Diolein Synthesis

Abstract

1,3-Diacylglycerol preparation has roused increasing attention in recent years as the 1,3-diacylglycerol-rich oils can suppress the deposition of visceral fat and prevent the body weight increasing. Lipozyme TL IM-mediated esterification of oleic acid with monoolein was effective for 1,3-diacylglycerol production. During the esterification process, the solvent shows obvious influence on the diolein synthesis as well as the 1,3-diolein production. This work investigated the related kinetics and mechanism of the solvent effect on the esterification and Lipozyme TL IM performance. The results indicated that both the esterification rate constant and the acyl migration rate constant positively correlated with the log P of the solvent, while the site specificity of lipase has negative correlation with solvent log P . The acylation toward the 2-position of 1-monoolein was more sensitive to the solvent log P compared to the 1-position of glycerides. Molecular dynamics simulation revealed that solvents with different log P influenced the structure of Lipozyme TL IM including RMSD, hydrogen bond, and radial distribution function to a large extent, which subsequently led to the catalytic activity and selectivity variation of the lipase.

Effect of Deep Eutectic Mixtures in Hydroxylation of Fatty Acids: A Correlation between Water Activity and Thermostability of FA-HY1

“…The flexibilities of FA-HY1 in different systems were also measured with RMSF, which could be used as a parameter reflecting the structure and function of enzymes. , Figure b illustrates the calculation of RMSF values by using trajectory data, followed by the convergence of the RMSD values of several systems. It is important to notice that the majority of RMSF values are under 1 Å.…”

Insight into the medium‐long‐medium structured lipids made from Camellia oil: Composition–structure relationship

“…They can change the configuration of enzymes in active site and lipase lid, respectively. (Huang et al, 2022a(Huang et al, , 2022cZitian et al, 2020). Although Novozym 435 is a lipase that acts as non-1,3 specific, when a great excess of ethanol is used, this lipase acts as 1,3-specific (Muñío et al, 2009).…”

Progress and perspectives of enzymatic preparation of human milk fat substitutes

“…It was reported that in many cases lipases expressed higher catalytic activity but lower sn-1,3 selectivity with increasing log P of the solvents [89][90][91]. Bi et al [90] found that Candida sp.…”

“…Duan et al [89] observed the similar phenomenon when using Novozym 435 as the biocatalyst. The solvent effect on the regioselectivity was thought to be attributed to the variation of binding energy between lipase and different positions of hydroxyl groups [89][90][91]. On the contrary, whole-cell lipase from Aspergillus niger GZUF36 was found to exhibit stronger sn-1,3 selectivity in the solvent with higher log P value [92].…”

“…On the contrary, whole-cell lipase from Aspergillus niger GZUF36 was found to exhibit stronger sn-1,3 selectivity in the solvent with higher log P value [92]. In some studies it was found that solvent can inhibit acyl migration, especially solvents with high log P, and adopting polar solvent as the reaction medium or adding a small amount of water was proposed for inhibiting the acyl migration [26,36,91]. While Wang et al [93] revealed that the isomerization of 2-MAG was much faster in solvent-free system and t-butanol expressed obvious inhibition on the acyl migration.…”