Abstract
Through proper selection of initial conditions and control of the reaction medium composition, a productivity rate over 10-fold higher than that previously reported was achieved for lipase-catalyzed fructose-oleic acid esterification. From a screening process, tert-butanol (t-BuOH) was selected as the most effective solvent for cosolubilizing fructose and oleic acid during the initial stage of the reaction. A t-BuOH concentration of 0.35–0.55 w/w produced the highest rate and extent of reaction at 60°C. Neither water addition nor removal applied to initial reaction materials improved the rate. Since both fructose-oleic acid mono- and diester promoted higher fructose solubility than either oleic acid or oleic acid/t-BuOH mixtures, t-BuOH was not needed during the latter stage of the reaction. Also, the presence of t-BuOH hindered the removal of water by free evaporation. Thus, complete removal of t-BuOH during the middle-to-latter stage of reaction was found to enhance the reaction rate. In addition, the introduction of fructose to the reactor in small batchwise increments accelerated the reaction. The monoester to diester ratio decreased during the initial and middle stages of the reaction owing to the disappearance of t-BuOH, but increased slightly during the later stages presumably because of the ester formation.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Nakamura, S., Using Sucrose Esters as Food Additives, INFORM 8:866–874 (1997).
Vulfson, E., Enzymatic Synthesis of Surfactants, in Novel Surfactants: Preparation, Applications, and Biodegradability, Surfactant Science Series, edited by K. Holmberg, Marcel Dekker, New York, 1998, Vol. 74, pp. 279–300.
Tushima, R., and S. Tagata, Surfactants from Natural Fats and Oils, INFORM 4:680–693 (1993).
Ducret, A., A. Giroux, M. Trani, and R. Lortie, Characterization of Enzymatically Prepared Biosurfactants, J. Am. Oil Chem. Soc. 73:109–113 (1996).
Fregapane, G., D.B. Sarney, S.G. Greenberg, D.J. Knight, and E.N. Vulfson, Enzymatic Synthesis of Monosaccharide Fatty Acid Esters and Their Comparison with Conventional Products, Ibid.:87–91 (1994).
Woudenberg-van Oosterom, M., F. van Rantwijk, and R.A. Sheldon, Regioselective Acylation of Disaccharides in tert-Butyl Alcohol Catalyzed by Candida antarctica Lipase, Biotechnol. Bioeng. 49:328–333 (1996).
Sarney, D.B., M.J. Barnard, D.A. MacManus, and E.N. Vulfson, Application of Lipases to the Regioselective Synthesis of Sucrose Fatty Acid Monoesters, J. Am. Oil Chem. Soc. 73:1481–1487 (1996).
Kim, J.J., J.J. Han, J.H. Yoon, and J.S. Rhee, Effect of Salt Hydrate Pair on Lipase-Catalyzed Regioselective Monoacylation of Sucrose, Biotechnol. Bioeng. 57:121–125 (1998).
Laane, C., S. Boeren, K. Vos, and C. Veeger, Rules for Optimization of Biocatalysis in Organic Solvents, Ibid.:81–87 (1987).
Stevenson, D.E., R.A. Stanley, and R.H. Furneaux, Glycerolysis of Tallow with Immobilized Lipase, Biotechnol. Lett. 15:1043–1048 (1993).
Cao, L., A. Fischer, U.T. Bornscheuer, and R.D. Schmid, Lipase-Catalyzed Solid Phase Synthesis of Sugar Fatty Acid Esters, Biocatal. Biotransform. 14:269–283 (1997).
Hayes, D.G., and R. Kleiman, Lipase-Catalyzed Synthesis of Lesquerolic Acid Wax Esters and Their Properties, J. Am. Oil Chem. Soc. 73:1385–1392 (1996).
Khaled, N., D. Montet, M. Pina, and J. Graille, Fructose Oleate Synthesis in a Fixed Catalyst Bed Reactor, Biotechnol. Lett. 13:167–172 (1991).
Ducret, A., A. Giroux, M. Trani, and R. Lortie, Enzymatic Preparation of Biosurfactants from Sugars or Sugar Alcohols and Fatty Acids in Organic Media Under Reduced Pressure, Biotechnol. Bioeng. 48:214–221 (1995).
Guillardeau, L., D. Montet, N. Khaled, M. Pina, and J. Graille, Fructose Caprylate Biosynthesis in a Solvent-Free Medium, Tenside Surfactants Deterg. 29:342–344 (1992).
Ward, O.P., J. Fang, and Z. Li, Lipase-Catalyzed Synthesis of a Sugar Ester Containing Arachidonic Acid, Enzyme Microb. Technol. 20:52–56 (1997).
McKeigue, K., and E. Gulari, Effect of Molecular Association on Diffusion in Binary Liquid Mixtures, AIChE J. 35:300–310 (1989).
Janssen, A.E.M., A. van der Padt, H.M. van Sonsbeek, and K. van’t Riet, The Effect of Organic Solvents on the Equilibrium Position of Enzymatic Acylglycerol Synthesis, Biotechnol. Bioeng. 41:95–103 (1993).
Valivety, R.H., P.J. Halling, and A.R. Macrae, Reaction Rate with Suspended Lipase Catalyst Shows Similar Dependence on Water Activity in Different Organic Solvents, Biochim. Biophys. Acta 1118:218–222 (1992).
Ferreira-Dias, S., and M.M.R. da Fonseca, Production of Monoglycerides by Glycerolysis of Olive Oil with Immobilized Lipases: Effect of the Water Activity, Bioprocess Eng. 12:327–337 (1995).
Mensah, P., J.L. Gainer, and G. Carta, Adsorptive Control of Water in Esterification with Immobilized Enzymes: I. Batch Reactor Behavior, Biotechnol. Bioeng. 60:434–444 (1998).
Sarney, D.B., M.J. Barnard, M. Virto, and E.N. Vulfson, Enzymatic Synthesis of Sorbitan Esters Using a Low-Boiling-Point Azeotrope as a Reaction Solvent, Biotechnol. Bioeng. 54:351–356 (1997).
Scheckermann, C., A. Schlotterbeck, M. Schmidt, V. Wray, and S. Lang, Enzymatic Monoacylation of Fructose by Two Procedures, Enzyme Microb. Technol. 17:157–162 (1995).
Warwel, S., and M. Rüsch gen. Klaas, Chemo-Enzymatic Epoxidation of Unsaturated Carboxylic Acids, J. Molec. Catal. B 1:29–35 (1995).
Author information
Authors and Affiliations
Corresponding author
About this article
Cite this article
Zhang, X., Hayes, D.G. Increased rate of lipase-catalyzed saccharide-fatty acid esterification by control of reaction medium. J Amer Oil Chem Soc 76, 1495–1500 (1999). https://doi.org/10.1007/s11746-999-0191-3
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/s11746-999-0191-3