Fatty lipase-catalyzed synthesis

Nagao, A. and Kite, M. (1990) Lipase-catalyzed synthesis of fatty acid esters useful in the food industry. Biocatalysis, 3, 295-305. 

Soumanou, M. M., and Bornscheuer, U. T. 2003. Improvement in lipase-catalyzed synthesis of fatty acid methyl esters from sunflower oil. Enzyme and Microb. Technol, 33, 97-103. 

Fig. 8.38 Lipase-catalyzed synthesis of fatty acid esters.

Effect of Acyl Donors. TTie synthesis of glucose fatty acid esters was investigated with continuous by-product removal in a stirred-tank membrane reactor by azeotropic distillation using EMK containing 20% hexane as reaction solvent and different fatty acids as acyl donors. From previous studies on the lipase-catalyzed synthesis of glucose esters in a solid-phase system (17,19,22,23), it was already known that the fatty acid chainlength had a considerable influence on product formation. This was due... 

Yan, Y., U.T. Bornscheuer, and R.D. Schmid, Lipase-Catalyzed Synthesis of Vitamin C Fatty Acid Esters, Biotechnol. Lett. 21 1051-1054 (1999). 

Yamane, T. Lipase-catalyzed synthesis of structured triacylglycerols containing polyunsaturated fatty acids monitoring the reaction and increasing the yield. In Enzymes in Lipid Modification Bornscheuer, U.T., Ed. Wiley-VCH Weinheim, Germany, 2000 148-169. 

Waldinger, C., and Schneider, M. 1992. Enzymatic synthesis of glycerol HI. Lipase-catalyzed synthesis of regioisomerically pure 1,3-iw-diacylglycerols and l(3)-rac-monoacylglycerols derived from unsaturated fatty acids. J. Am. Oil Chem. Soc. 69 1513-1519. 

As mentioned above, lipase-catalyzed synthesis of triglycerides from glycerol and fatty acids can be performed in fair yield in monolayer experiments [93,133]. Another air/water inter facial system, foam, also gave di- and triglycerides in higher yields than were obtained in microemulsions [134]. Reactions in foams may be of more practical interest than reactions in monolayers due to the much larger interfacial area in the former type of system. 

Sabeder, S Habulin, M Knez, Z. Lipase-catalyzed synthesis of fatty acid fructose esters. Journal of Food Engineering, 2006, v. 77 (4), 880-886. 

The fatty esters of polyethers are known to be good surfactants, and many commercial products are available in the market place. Most people use chemical methods to achieve the required synthesis. Enzymatic methods can also be used however, the reaction needs to be optimized. An example is the lipase-catalyzed synthesis of fatty acid diester of poly(ethylene glycol) EG). 

Sabeder, S., M. Habulin, and Z. Knez. 2006. Lipase-Catalyzed Synthesis of Fatty Acid Fructose Esters. Journal of Food Engineering 77 (4) 880-886. 

The use of w/o microanulsions as media for the lipase-catalyzed synthesis of mono- and diesters of various hydrophilic diols which have nonionic surfactant properties suitable for cosmetic, pharmaceutical, and nutritional purposes was investigated [112,122,130,131]. In this system, relatively large quantities of hydrophilic diols can be solubilized and their selective esterification with various fatty acids can be achieved with very high reaction rates at room temperature. By controlling the reaction time and the concentration of the substrates it is possible to change the product distribution toward the preferential mono- or diesters of hydrophilic diols [122]. 

Figure 10.4 Bioreactor system operated under continuous recirculation, for the solvent-free lipase-catalyzed synthesis of saccharide-fatty acid esters (PBBR refers to "packed-bed bioreactor").

Ye R, Pyo S-H Hayes DG. 2010. Lipase-catalyzed synthesis of saccharide-fatty acid esters using suspensions of saccharide crystals in solvent-free media. Journal of the American Oil Chemists Society... 

Unlike chemical interesterification, the catalytic action of lipases is reversible. In aqueous conditions lipases promote lipolysis, whereas in a water-poor environment synthesis reactions predominate. Lipase-catalyzed synthesis reactions have been studied since the 1970s, when Tsujisaka et al. (1977) showed that lipases could catalyze the formation of TAGs from partial acylglycerols and free fatty acids. Hydrolysis reactions have been studied since the 1950s (Brocker-hoff and Jensen, 1974). 

Watanabe, Y., Adachi, S., Nakanishi, K. and Matsuno, R. (2001) Lipase-catalyzed synthesis of unsaturated acyl /-ascorbate and its ability to suppress the autoxidation of polyunsaturated fatty acid. J. Am. Oil Chem. Soc., 78, 823-826. 

Lee, S. H., Dang, D. T., Ha, S. H. et al. (2007) Lipase-catalyzed synthesis of fatty acid sugar esters using extremely supersaturated sugar solution in ionic hquids. Biotechnol. Bioeng., 99, 1-8. 

Ester synthesis of fatty acid ethyl ester. The lipase-catalyzed esterification of fatty acid and alcohol is well-known. It was also favorable for the esterification of poly unsaturated fatty acids under mild conditions with the enzyme. However, the activity of native lipase is lower in polar organic solvents, i.e. ethanol and methanol. The synthesis of Ae fatty acid ethyl ester was carried out in ethanol using the palmitic acid-modified lipase. As shown in Figure 7, the reactivity of the modified lipase in this system was much higher than that of the unmoditied lipase. 

Synthesis in the presence of undissolved substrates has proven useful also in the lipase-catalyzed syntheses of surfactants such as glucose esterified with fatty acids or esters of glycosides [71], but also in more unusual examples such as ibuprofen resolution [72] and the syntheses of the cinnamic alcohol ester of glucuronic acid... 

Once bearing some substituents, the decrease of polarity of the sucrose derivatives makes them soluble in less-polar solvents, such as acetone or tert-butanol, in which some lipases are able to catalyze esterifications. Unlike proteases, which necessitate most often the use of an activated acyl donor (such as vinyl or trifluoroethyl esters), lipases are active with simple esters and even the parent carboxylic acids in the presence of a water scavenger. The selectivity of the lipase-catalyzed second esterification is specific for OH-6 allowing the synthesis of mixed T,6 -diesters.123,124 For some lipases, a chain-length dependence on the regiochemistry was observed.125 Selectively substituted monoesters were thus prepared and studied for their solution and thermotropic behavior.126,127 Combinations of enzyme-mediated and purely chemical esterifications led to a series of specifically substituted sucrose fatty acid diesters with variations in the chain length, the level of saturation, and the position on the sugar backbone. This allowed the impact of structural variations on thermotropic properties to be demonstrated (compare Section III.l).128... 

Hydrolytic enzymes such as lipases catalyze hydrolysis of esters in aqueous media, but when used in non-aqueous media such as organic solvents, ionic liquids and supercritical fluids, they catalyze reverse reactions the synthesis of esters. For example, lipases in natural environment catalyze the hydrolysis of fatty acid esters as shown in Figure 6(a). However, when they are used in organic solvents, they catalyze the esterification reaction (Figure 6(b)). 

In the interesterification of fats, 1,3-positional specific lipases catalyze reactions in which only the fatty acids in the a-positions of the triglycerides take part, whereas positional nonspecific lipases are able to catalyze reactions in which the fatty acids from both the a- and / -positions take part. In transesterification between two types of fat, the positional non-specific lipase is therefore able to randomize the fatty acids, resulting in the same fatty acid composition in the triglycerides as obtained in the commercially important chemical randomization process. In ester synthesis, positional non-specific lipases catalyze the reaction with both primary and secondary alcohols whereas positional specific lipases are more or less specific for primary alcohols. 

Application of Crystallization Technique for the Lipase-Catalyzed Solid-Phase Synthesis of Sugar Fatty Acid Monoesters... 

Ganske F, Bomscheuer UT (2005) Optimization of lipase-catalyzed glucose fatty acid ester synthesis in a two-phase system containing ionic liquids and t-BuOH. J Mol Catal B Enzym 36 40 2... 

The solvent also influences the reaction through its effect on the relative soln-bility of substrate and product. Ideally, the substrate would be solubilized, while the insoluble product precipitates from solution. Thus, the recovery of product would be improved, thermodynamic equilibrium in the solvent phase would be driven toward ester synthesis, and product inhibition would be prevented. This scenario can occur for the lipase-catalyzed esterification of saccharides and nonpolar, saturated fatty acids. When employing polar solvents such as acetone, saccharides remain solubilized, while the product, saccharide-fatty acid monoester, precipitated. ... 

Cao, L., Fischer, A., Bomscheuer, U. T., and Schmid, R. D., Lipase-catalyzed sohd phase synthesis of sugar fatty acid esters. Biocat. Biotrans., 14 269-283, 1997. 

FIG. 3 Hydroperoxy-fatty acid synthesis from triacylglycerol with successive lipase-catalyzed hydrolysis and lipoxygenation. 

In the enzymatic process utilized herein for the production of fatty acid methyl ester fixrm rapeseed oil, several factors are known to influence conversion. The initial step of this study involved the identification of factors likely to influence conversion, fri this study, tert-butanol was applied in lipase-catalyzed methanolysis. fert-Butanol has been utilized previously in several enzymatic process, including sorbitan ester synthesis [6, 15]. It has also been confirmed that terf-butanol is inert in the Novozym 435-catalyzed methanolysis of rapeseed oil for the production of biodiesel [12]. 

Lamare S, Legoy M (1993) Biocatalysis in the gas phase. TIBTECH 11 413 18 Laudani CG, Habulin M, Knez 2 et al. (2007) Lipase-catalyzed long chtiin fatty ester synthesis in dense carbon dioxide kinetics and thermodynamics. J Supercritical Fluids 41 92-101 Lauwers A, Scharpe S (1997) Pharmaceutical enzymes. Marcel Dekker, New York, 401 pp Laval JM, Thomas D, Mazeran PE (2000) Nanobiotechnology and its role in the development of new analytical devices. Analyst 125 29-3... 

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