The mechanism of solvent effect on the positional selectivity of Candida antarctica lipase B during 1,3-diolein synthesis by esterification

Duan, Zhiguang; Liu, Dehua

doi:10.1016/j.biortech.2011.09.003

Cited by 24 publications

(16 citation statements)

References 21 publications

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“…This reaction is responsible for the generation of undesired isomers during the synthesis of acyl glycerides [11][12]. But in turn, it is a desired reaction during the production of biodiesel, because most of the lipases used in this synthesis act at a specific position on the glycerol backbone [13][14][15]. If not for acyl migration, biodiesel yields would not exceed 66% and they would be high in monoglycerides.…”

Section: Introductionmentioning

confidence: 99%

An insight on acyl migration in solvent-free ethanolysis of model triglycerides using Novozym 435

Sánchez

Tonetto

Ferreira

2016

Journal of Biotechnology

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In this work, the ethanolysis of triglycerides catalyzed by immobilized lipase was studied, focusing on the secondary reaction of acyl migration. The catalytic tests were performed in a solvent-free reaction medium using Novozym 435 as biocatalyst. The selected experimental variables were biocatalyst loading (5-20mg), reaction time (30-90min), and chain length of the fatty acids in triglycerides with and without unsaturation (short (triacetin), medium (tricaprylin) and long (tripalmitin/triolein)). The formation of 2-monoglyceride by ethanolysis of triglycerides was favored by long reaction times and large biocatalyst loading with saturated short- to medium-chain triglycerides. In the case of long-chain triglycerides, the formation of this monoglyceride was widely limited by acyl migration. In turn, acyl migration increased the yield of ethyl esters and minimized the content of monoglycerides and diglycerides. Thus, the enzymatic synthesis of biodiesel was favored by long-chain triglycerides (which favor the acyl migration), long reaction times and large biocatalyst loading. The conversion of acylglycerides made from long-chain fatty acids with unsaturation was relatively low due to limitations in their access to the active site of the lipase.

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Section: Introductionmentioning

confidence: 99%

An insight on acyl migration in solvent-free ethanolysis of model triglycerides using Novozym 435

Sánchez

Tonetto

Ferreira

2016

Journal of Biotechnology

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“…It has been reported that Novozym 435 acts as non‐specific lipase when enzymatic esterification between glycerol and free fatty acid is conducted in solvent‐free system or hexane . However, when the esterification reaction between glycerol and free fatty acid is carried out in t ‐butanol system, the Novozym 435 tends to act as 1,3‐specific lipase . In addition, acyl donor also affects the selectivity of Novozym 435 lipase.…”

Section: Resultsmentioning

confidence: 99%

Scalable synthesis of highly pure 2‐monoolein by enzymatic ethanolysis

Wang

Liang

et al. 2014

Euro J Lipid Sci & Tech

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It has been reported that 2-monoolein exhibits various biological activities. In this study, an enzymatic method is reported for the synthesis of highly pure 2-monoolein by ethanolysis of oleic acid-rich oil. The effects of solvent type, addition amounts of solvent and lipase, and reaction time on 2-MAGs content in the crude reaction mixture were investigated. Under the optimized conditions, there was 37.6% (area/area) 2-MAGs produced in the crude mixture. 2-MAGs were obtained at 97-98% purity and 33.6% yield (w/w) after fractionation in 85% ethanol aqueous solution and hexane to fully remove impurities including DAGs, TAGs, and fatty acid ethyl esters. Subsequently, 2-MAGs were purified further by two-step crystallization in hexane to remove saturated and polyunsaturated 2-MAGs to obtain pure 2-monoolein. After the two-step crystallization, 97.5% 2-monoolein was obtained at 78.3% yield (w/w). Compared to previous methods, our method for the synthesis of 2-monoolein is easier to scale up, obtain highly pure 2-monoolein product and more economical. In addition, the study on the effect of solvent type suggests that selectivity of the lipase and acyl migration of 2-MAGs may be affected by reaction solvent polarity.Practical application: Synthetic 2-monoolein can be used as emulsifier and surfactant in food, pharmaceutical and cosmetic and other industries. In addition, 2-monoolein has exhibited strong antioxidation and anti-atherosclerotic properties in vitro and in a cellular model. Thus, 2-monoolein has potential application in treating cardiovascular diseases.

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“…Considering energy cost, when an industrial preparation of 1,3-diolein is performed by this method, 25 °C may be more suitable. Generally, the reaction for the synthesis of 1,3-DAG by the esterification of free fatty acids with glycerol is usually conducted at 60-70 °C in order to keep a high lipase activity [26,27], but, the resultant 1,3-DAG concentration in the crude reaction mixture by this method is low (40-50 %), probably due to reversibility of the esterification reaction. Esterification conducted at a temperature higher than 60 °C is unfavorable due to the acyl migration of 1,3-DAG to 1,2-DAG.…”

Section: Effect Of Reaction Temperaturementioning

confidence: 99%

Preparation of 1,3‐Diolein by Irreversible Acylation

Wang

Han

Zou

et al. 2014

J Americ Oil Chem Soc

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Earlier findings on the nutritional benefits of diacylglycerols (DAGs) have attracted much attention on the synthesis of DAGs. In this study, we reported an improved method for the lipase-catalyzed synthesis of 1,3-diolein by the irreversible glycerolysis of vinyl oleate with glycerol. The effects of reaction system, lipase loading, molar ratio of vinyl oleate to glycerol, reaction temperature and time on 1,3-diolein content in crude reaction mixture were investigated. When the reaction was conducted in a solvent-free system at 30 °C for 8 h by reacting 2 mmol vinyl oleate with 1 mmol glycerol with 8 % (w/w, relative to total reactants) Lipozyme RM IM (Novozymes, Beijing, China) as catalyst, there were 90.5 ± 2.9 % (area/area) 1,3-diolein and (3.3 ± 0.3) % 1,2-diolein produced. After purification, 1,3-diolein was obtained at 81.4 % yield with 98.2 % purity. The lipase-catalyzed synthesis of 1,3-diolein using vinyl oleate as acyl donor by glycerolysis was also conducted using a medium with 50 mmol of glycerol and 100 mmol vinyl oleate. Compared to enzymatic esterification in a solvent, enzymatic glycerolysis for the synthesis 1,3-diolein is more effective due to the irreversible reaction, mild due to the low reaction temperature, and environmentally benign due to the use of solvent-free reaction system.

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The mechanism of solvent effect on the positional selectivity of Candida antarctica lipase B during 1,3-diolein synthesis by esterification

Cited by 24 publications

References 21 publications

An insight on acyl migration in solvent-free ethanolysis of model triglycerides using Novozym 435

An insight on acyl migration in solvent-free ethanolysis of model triglycerides using Novozym 435

Scalable synthesis of highly pure 2‐monoolein by enzymatic ethanolysis

Preparation of 1,3‐Diolein by Irreversible Acylation

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