Double Immobilized Lipase for the Kinetic Resolution of Secondary Alcohols
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.
[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.
[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.
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:60508", author = "A. Ursoiu and C. Paul and C. Marcu and M. Ungurean and F. Péter", title = "Double Immobilized Lipase for the Kinetic Resolution of Secondary Alcohols", 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.", volume = "5", number = "4", pages = "364-5", }
