Acyl Group Migrations in 2-Monoolein

Millqvist‐Fureby, Anna; Virto, Carmen; Adlercreutz, Patrick; Mattìasson, Bo

doi:10.3109/10242429609106879

Cited by 99 publications

(77 citation statements)

References 27 publications

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“…At longer reaction times, acyl migration becomes important and the amount of the 1,3-DAG isomer increases in the glycerolysis mixture. Acids, bases, and heat can promote acyl migration (29). Accordingly, the enzyme carrier can also affect acyl migration if it has an acidic or basic surface, such as silica, celite, and ion-exchange resins.…”

Section: Resultsmentioning

confidence: 99%

Diacylglycerol synthesis by enzymatic glycerolysis: Screening of commercially available lipases

Kristensen

2005

J Americ Oil Chem Soc

108

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Seven lipases were screened for their ability to synthesize DAG in the glycerolysis of rapeseed oil. In batch reactions with free glycerol, the lipase carrier was of great importance for catalysis. Catalysis did not take place in reactions with lipases having hydrophilic carriers. The best DAG yield (approx. 60 wt%) was achieved with Novozym 435 and Lipase PS-D after 7 h, and an equilibrium was obtained. Stepwise addition of glycerol allowed catalysis with Novozym CALB L (immobilized) to take place in spite of the hydrophilic carrier; however, the DAG yield was only 19 wt%. This result suggests that glycerol forms a layer around the hydrophilic lipase particles, limiting contact between the lipases and the hydrophobic oil phase. With glycerol absorbed on silica gel, all lipases catalyzed the glycerolysis reaction. Faster conversion of TAG was obtained with Lipase PS-D, Lipase AK, and Lipase F-AP15 than in reactions with free glycerol, but the DAG yield remained approximately 60-65 wt%. Nonspecific lipases yielded more 1,3-DAG early in the reaction.Paper no. J10954 in JAOCS 82, 329-334 (May 2005).

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Section: Resultsmentioning

confidence: 99%

Diacylglycerol synthesis by enzymatic glycerolysis: Screening of commercially available lipases

Kristensen

2005

J Americ Oil Chem Soc

108

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“…Similarly, the equilibrium constant between 1-acyl glycerol and 2-acyl glycerol is 9.0 (Fureby et al, 1996). Thus, the esteri®ca-tion of the sn-1 position of glycerol is thermodynamically favored over the esteri®cation of the sn-2 position.…”

Section: Different Synthesis Routes To Mixed Chain Phospholipidsmentioning

confidence: 85%

Synthesis of phosphatidylcholine with defined fatty acid in the sn‐1 position by lipase‐catalyzed esterification and transesterification reaction

Adlercreutz

Budde

Wehtje

2002

Biotech & Bioengineering

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The incorporation of caproic acid in the sn-1 position of phosphatidylcholine (PC) catalyzed by lipase from Rhizopus oryzae was investigated in a water activity-controlled organic medium. The reaction was carried out either as esterification or transesterification. A comparison between these two reaction modes was made with regard to product yield, product purity, reaction time, and byproduct formation as a consequence of acyl migration. The yield in the esterification and transesterification reaction was the same under identical conditions. The highest yield (78%) was obtained at a water activity (a(w)) of 0.11 and a caproic acid concentration of 0.8 M. The reaction time was shorter in the esterification reaction than in the transesterification reaction. The difference in reaction time was especially pronounced at low water activities and high fatty acid concentrations. The loss in yield due to acyl migration and consequent enzymatic side reactions was around 16% under a wide range of conditions. The incorporation of a fatty acid in the sn-1 position of PC proved to be thermodynamically much more favorable than the incorporation of a fatty acid in the sn-2 position.

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“…Irimescu et al [7] demonstrates that 2-MAG can be synthesized and isolated in high 2-MAG:1-MAG ratios (>9:1) through the regiospecific ethanolysis of TAG catalyzed by Novozym 435 (immobilized Candida antartica lipase B) using large excesses of ethanol. The rate of acyl migration of 2-MAG to1-MAG, and thus the purity of 2-MAG, is affected by temperature, solvent, and acid and base impurities, which catalyze the migration [4]. Previous studies indicate that the acyl migration of MAG reaches an equilibrium resulting in a 2-MAG:1-MAG ratio of~1:9 [8,9].…”

Section: Introductionmentioning

confidence: 98%

“…Additionally, 2-monoacylglycerols (2-MAG) are convenient reagents for the synthesis of structured lipids [3] although acyl migration often hampers the formation of specific positional isomers [4,5]. 2-MAG acyl migration is also a cornerstone of understanding the chemistry of lipid metabolism [6].…”

Section: Introductionmentioning

confidence: 99%

Acyl Migration Kinetics of 2‐Monoacylglycerols from Soybean Oil via ¹H NMR

Compton

Vermillion

Laszlo

2007

J Americ Oil Chem Soc

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The acyl migration kinetics of neat 2-monoacylglycerol (2-MAG) to form 1-MAG was determined using 1 H NMR spectroscopy to monitor the b-proton integration ratios of the two species over time. 2-MAG was synthesized by the Novozym 435-catalyzed alcoholysis of soybean oil and isolated by solvent extraction or molecular distillation at a mole fraction (X 2-MAG ) of 0.94 relative to total MAG. The kinetics parameters of the neat 2-MAG acyl migration were investigated over the temperature range of 23-80°C. The 2-MAG mol fraction remained unchanged at 23°C over the course of 168 h and reached an equilibrium of X 2-MAG = 0.09 at only 80°C. Modeling of the kinetics data revealed a 2-MAG half life (t 1/2 ) of 3,500 and 22.8 h at 23 and 80°C, respectively, with an activation energy of 79.0 ± 6.5 kJ mol -1 . The use of 1 H NMR spectroscopy proved an expedient method for monitoring the acyl migration in 2-MAG compared to other reported methods (e.g. GC, HPLC, and 13 C-NMR spectroscopy), requiring no sample manipulation and minimizing the deleterious effects of high temperatures and solvent exposure.

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Acyl Group Migrations in 2-Monoolein

Cited by 99 publications

References 27 publications

Diacylglycerol synthesis by enzymatic glycerolysis: Screening of commercially available lipases

Diacylglycerol synthesis by enzymatic glycerolysis: Screening of commercially available lipases

Synthesis of phosphatidylcholine with defined fatty acid in the sn‐1 position by lipase‐catalyzed esterification and transesterification reaction

Acyl Migration Kinetics of 2‐Monoacylglycerols from Soybean Oil via ¹H NMR

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Acyl Group Migrations in 2-Monoolein

Cited by 99 publications

References 27 publications

Diacylglycerol synthesis by enzymatic glycerolysis: Screening of commercially available lipases

Diacylglycerol synthesis by enzymatic glycerolysis: Screening of commercially available lipases

Synthesis of phosphatidylcholine with defined fatty acid in the sn‐1 position by lipase‐catalyzed esterification and transesterification reaction

Acyl Migration Kinetics of 2‐Monoacylglycerols from Soybean Oil via 1H NMR

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Acyl Migration Kinetics of 2‐Monoacylglycerols from Soybean Oil via ¹H NMR