Double Immobilized Lipase for the Kinetic Resolution of Secondary Alcohols

Authors: A. Ursoiu, C. Paul, C. Marcu, M. Ungurean, F. Péter

Abstract:

Sol-gel immobilization of enzymes, which can improve considerably their properties, is now one of the most used techniques. By deposition of the entrapped lipase on a solid support, a new and improved biocatalyst was obtained, which can be used with excellent results in acylation reactions. In this paper, lipase B from Candida antarctica was double immobilized on different adsorbents. These biocatalysts were employed in the kinetic resolution of several aliphatic secondary alcohols in organic medium. High total recovery yields of enzymatic activity, up to 560%, were obtained. For all the studied alcohols the enantiomeric ratios E were over 200. The influence of the reaction medium was studied for the kinetic resolution of 2-pentanol.

Keywords: Double immobilization, enantioselectivity, kineticresolution, lipase, racemates, sol-gel entrapment.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1077345

References:

[1] T. Raghavendra, D. Sayania, and D. Madamwar, "Synthesis of the "green apple ester" ethyl valerate in organic solvents by Candida rugosa lipase immobilized in MBGs in organic solvents: Effects of immobilization and reaction parameters", Journal of Molecular Catalysis B: Enzymatic, vol. 63, 2010, pp. 31-38.
[2] Y. Mine, L. Zhang, K. Fukunaga, and Y. Sugimura, "Enhancement of enzyme activity and enantioselectivity by cyclopentyl methyl ether in the transesterification catalyzed by Pseudomonas cepacia lipase colyophilized with cyclodextrins", Biotechnology Letters, vol. 27, 2005, pp. 383-388.
[3] A. G. Cunha, A. T. da Silva, A. J. R. da Silva, L. W. Tinoco, R. V. Almeida, R. B. de Alencastro, A. B. C. Simas, and D. M. G. Freire, "Efficient kinetic resolution of (┬▒)-1,2-O-benzyl-myo-inositol with the lipase B of Candida antarctica", Tetrahedron: Asymmetry, vol. 21, 2010, pp. 2899-2903.
[4] J. H. Lee, K. Han, M.-J. Kim, and J. Park, "Chemoenzymatic Kinetic Resolution of Alcohols and Amines", European Journal of Organic Chemistry, 2010, pp. 999-1015.
[5] V. Gotor-Fernandez, R. Brieva, and V.Gotor, "Useful biocatalysts for the preparation of pharmaceuticals", Journal of Molecular Catalysis B: Enzymatic, vol. 40, 2006, pp. 111-120.
[6] H.-M. Chen, P.-Y. Wang, and S.-W. Tsai, "Carica papaya lipasecatalyzed transesterification resolution of secandary alcohols in organic solvents", Journal of the Taiwan Institute of Chemical Engineers, vol. 40, 2009, pp. 594-554.
[7] A. Tomin, D. Weiser, G. Hellner, Z. Bata, L. Cor├«ci, F. Péter, B. Koczka, and L. Poppe, "Fine-tuning the second generation sol-gel lipase immobilization with ternary alkoxysilane precursor systems", Process Biochemistry, vol. 46, 2011, pp. 52-58.
[8] N. Kharrat, Y. B. Ali, S. Marzouk, Y.-T. Gargouri, and M. Karra- Chaabouni, "immobilization of Rhizopus oryzae Lipase on silica aerogels by adsorption: Comparison with free enzyme", Process Biochemistry, 2011, doi:10.1016/j.procbio.2011.01.029.
[9] F. Peter, L. Poppe, C. Kiss, E. Szocs-Biro, G. Preda, C. Zarcula, and A. Olteanu, ÔÇ×Influence of precursors and additives on microbial lipases stabilized by sol-gel entrapment", Biocat. Biotrans., vol. 23, nr. 3/4, 2005, pp. 251-260.
[10] C. Zarcula, L. Cor├«ci, R. Croitoru, A. Ursoiu, and F. Péter, "Preparation and properties of xerogels obtained by ionic liquid incorporation during the immobilization of lipase by the sol-gel method", Journal of Molecular Catalysis B: Enzymatic, vol. 65, 2010, pp. 79-86.
[11] A. Uyanik, N. Sen, and M. Yilmaz, "Improvement of catalytic activity of lipase from Candida rugosa via sol-gel encapsulation in the presence of calix(aza)crown", Bioresource Technology, 2011, doi: 10.1016/j.biortech.2010.12.105.
[12] F. Péter, C. Paul, and A. Ursoiu, "Application of ionic liquids to increase the efficiency of lipase biocatalysis", in "Ionic Liquids: Applications and Perspectives", edited by Alexander Kokorin, 2011, ISBN: 978-953-307- 248-7, under publishing.
[13] C. Mateo, J. M. Palomo, G. Fernandez-Lorente, J. M. Guisan, and R. Fernandez-Lafuente, "Improvement of enzyme activity, stability and selectivity via immobilization techniques", Enzyme and Microbial Technology, vol. 40, 2007, pp. 1451-1463.
[14] H. P. Heldt-Hansen, M. Ishii, S. A. Patkar, T. T. Hansen, and P. Eigtved, "A new immobilized positional nonspecific lipase for fat modification and ester synthesis", ACS Symposium Series, vol. 389, 1989, pp. 158- 172.
[15] L. Brady, A. M. Brzozowski, Z. S. Derewenda, E. Dodson, G. Dodson, S. Tolley, J.P. Turkenburg, L. Christiansen, B. Huge-Jensen, L. Norskov, L. Thim, and U. Menge, "A serine protease triad forms the catalytic centre of a triacylglycerol lipase", Nature, vol. 343, 1990, pp. 767-770.
[16] C.-S. Chen, Y. Fujimoto, G. Girdauskas, and C. J. Sih, "Quantitative analyses of biochemical kinetic resolutions of enantiomers", Journal of the American Chemical Society, vol. 104, 1982, pp. 7294-7299.
[17] D. Zelaszczyk, and K. Kiec-Konowicz, "Biocatalytic Approaches to Optically Active β-Blockers", Current Medicinal Chemistry, vol. 14, 2007, pp. 53-65
[18] A. Ursoiu, C. Paul, C. Marcu, T. Péter, and F. Péter, "Binary and ternanry silane precursor systems for immobilization of lipases", Annals of West University of Timisoara, vol. 16, no. 2, 2010, pp. 17-22.
[19] C. Reichardt, "Solvatochromic Dyes as Solvent Polarity Indicators", Chem. Rev., vol. 94, 1994, pp. 2319-2358.