Solvent suitability for lipase-mediated acyl-transfer and esterification reactions in microaqueous milieu is related to substrate and product polarities

Yang, Baokang; Kuo, Shu-Jung; Hariyadi, Purwiyatno; Parkin, Kirk L.

doi:10.1016/0141-0229(94)90122-8

Cited by 28 publications

(11 citation statements)

References 23 publications

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“…The only exception noted was for the Lipozyme reaction with 1,2-PD in apolar media, in which sn-l,3-selectivity, coupled with a general restriction in enzyme reactivity (and possibly, acyl migration), may account for the relative lack of fully acylated products. In this case, overall reactivity was optimum in solvents of intermediate log P values of 1-2, an observation clearly not in accord with the general rule for solvent selection (12)(13)(14)(15)(16), and one we have recorded previously with other reaction systems (18). To the extent that previous studies are relevant, our results with glycerol are consistent with earlier findings.…”

Section: Esterification Of Undecanoic Acid and Glycerol The Extent Ofsupporting

confidence: 66%

“…Thus, the foundation for the original general rule of using log P values for solvent selection may be embedded in the compatibility of polarities between reaction products and the selected solvents. Recently, two studies have questioned the generality of the log P rule for solvent selection on the basis that neither solvent apolarity nor water-miscibility is specifically relevant to microaqueous biocatalysis (17), and that solvent selection should be done within the context of the nature (polarity) of the substrates and products of the desired reaction (18). Interestingly, the originators of the general log P rule suggested that proper juxtapositioning of polarities of substrate, product, solvent, and enzyme-solvent interphase was important to process optimization (12); however, this consideration has generally received little attention in studies in this area.…”

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confidence: 99%

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Solvent polarity influences product selectivity of lipase‐mediated esterification reactions in microaqueous media

Kuo

Parkin

1996

J Americ Oil Chem Soc

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Esterification reactions were evaluated by using lipases fromRhizomucor miehei (Lipozyme IM20) andPseudomonas cepacia (PS‐30) with equimolar levels (1.77 mmol) of undecanoic acid and glycerol or 1,3‐propanediol (1,3‐PD) or 1,2‐propanediol (1,2‐PD) in organic solvents of log P (partition coefficient between 1‐octanol/water) values of (−0.33–4.5. Reaction yields (percentage of esterified undercanoate) with glycerol ranged from 1.4 to 72%, with greatest yields observed in solvents of log P 4.0–4.5 for Lipozyme, whereas the PS‐30 lipase was similarly effective (27–38% yield) over the full range of solvent polarities. For both enzymes, as solvent apolarity increased, so did the extent of acylation of glycerol in the final product mixture. Reaction yields with 1,3‐PD ranged from 8.1 to 64% for Lipozyme and from 18 to 84% for PS‐30 lipase, with greatest yields observed for both enzymes in solvents of log P values in the range 1.2–5.0. For both lipases, the shift to greater solvent apolarity was accompanied by an increased molar ratio of diacylated‐1,3‐PD/monoacylated‐1,3‐PD in the product mixture. Reaction yields with 1,2‐PD ranged from 2.5 to 45% for Lipozyme and from 12 to 52% for PS‐30 lipase, with greatest yields observed in solvents of log P values in the ranges 1.4–1.9 and 1.4–4.5, respectively. The shift to greater solvent apolarity was accompanied by an increased molar ratio of diacylated‐1,2‐PD: monoacylated‐1,2‐PD in the product mixture, except for Lipozyme in the three most apolar solvents (log P of 3.5–4.5) in which there was a general attenuation of activity. These results suggest the existence of a solvent polarity influence on reaction product selectivity in multiproduct reactions, which can be partially explained on the basis of differential solvation and extraction properties of solvents.

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Section: Esterification Of Undecanoic Acid and Glycerol The Extent Ofsupporting

confidence: 66%

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confidence: 99%

Solvent polarity influences product selectivity of lipase‐mediated esterification reactions in microaqueous media

Kuo

Parkin

1996

J Americ Oil Chem Soc

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“…This reaction results in the isomerization of partial glycerides. Acyl migration is promoted by several factors: temperature [11,14], solvent polarity [14,15], presence of acids or bases [16] and silica gel [6,17]. The last step of the proposed process consists of facilitating acyl migration on the DAG mixture to increase the proportion of 1,3-DAG.…”

Section: A Process For Short-chain Dag-rich Milk Fatmentioning

confidence: 99%

A process for the production of a diacylglycerol‐based milk fat analogue

Lubary

Hofland

Horst

2010

Euro J Lipid Sci & Tech

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We propose a novel process for the production of a DAG-rich acylglycerol mixture derived from milk fat. This product has potentially interesting nutritional properties, derived from both its high content of DAG and of short-chain fatty acids (FAs). The proposed process consists of three steps: lipase-catalysed partial ethanolysis of milk fat, extraction of the by-product fatty acid ethyl esters (FAEEs) using supercritical carbon dioxide (SC-CO 2 ) and isomerization of DAG to increase the proportion of 1,3-DAG. The experimental investigation of the process steps was done using milk fat and trilaurin. Several lipases were tested for maximizing the percentage of DAG in the acylglycerol mixture produced by ethanolysis. The selectivity of the chosen lipase was such that the produced AG mixture was enriched in short-chain FAs in relation to the original milk fat. FAEEs were completely extracted from the ethanolysis mixture by SC-CO 2 . In the final process step, we explored the reaction conditions for facilitating acyl migration in the DAG mixture, so that the equilibrium proportion of 1,3-DAG (64%) was attained. Our results set the basis for the development of a simple process for the production of a DAG-rich milk fat analogue.

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“…According to Reslow et al (1987), the best solvents for esterification reaction were those with log P in the range of 1.5-2.1, confirming the results herein presented. As well documented, the choice of solvents for biocatalytic processes should be made in cognizance of the relative polarity of substrates and products of the reaction (Yang et al, 1994), the choice of the pressure condition likewise. The esterification reaction performance rise with pressure up to 10 MPa likely reflects the sharp increase in the hydrophobicity of CO 2 at higher pressures.…”

Section: Relationship Between Log P and Pressurementioning

confidence: 99%

Exploiting the pressure effect on lipase‐catalyzed wax ester synthesis in dense carbon dioxide

Knez

Laudani

Habulin

et al. 2007

Biotech & Bioengineering

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The present work focuses on the thermodynamic interpretation of the lauryl oleate biosynthesis in high-pressure carbon dioxide. Lipase-catalyzed lauryl oleate production by oleic acid esterification with 1-dodecanol over immobilized lipase from Rhizomucor miehei (Lipozyme RM IM) was successfully performed in a sapphire window batch stirred tank reactor (BSTR) using dense CO(2) as reaction medium. The experiments were planned to elucidate the pressure effect on the reaction performance. With increasing the pressure up to 10 MPa, the catalytic efficiency of the studied enzyme improved rising up to a maximum and decreased at higher pressure values. Kinetic observations, exhibiting that dense CO(2) expanded reaction mixture in subcritical conditions led to higher performance than when diluted in a single supercritical phase, were elucidated by phase-equilibrium arguments. The experimental results were justified with emphasis on thermodynamic interpretation of the studied system. Particularly, the different reaction performances obtained were related to the position of the operating point with respect to the location of liquid-vapor phase boundaries of the reactant fatty acid/alcohol/CO(2) ternary system. The outlook for exploitation of CO(2) expanded phase at lower pressure compared to supercritical phase, with heterogeneous system in which the solid catalyst particles are exposed to dense CO(2) expanded reaction mixture, in developing new biotransformation schemes is promising.

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Solvent suitability for lipase-mediated acyl-transfer and esterification reactions in microaqueous milieu is related to substrate and product polarities

Cited by 28 publications

References 23 publications

Solvent polarity influences product selectivity of lipase‐mediated esterification reactions in microaqueous media

Solvent polarity influences product selectivity of lipase‐mediated esterification reactions in microaqueous media

A process for the production of a diacylglycerol‐based milk fat analogue

Exploiting the pressure effect on lipase‐catalyzed wax ester synthesis in dense carbon dioxide

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