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Article

Regioselective and Stereoselective Epoxidation of n-3 and n-6 Fatty Acids by Fungal Peroxygenases

1
Instituto de Recursos Naturales y Agrobiología de Sevilla (IRNAS), Consejo Superior de Investigaciones Científicas (CSIC), Reina Mercedes 10, E-41012 Seville, Spain
2
Centro de Investigaciones Biológicas “Margarita Salas” (CIB), Consejo Superior de Investigaciones Científicas (CSIC), Ramiro de Maeztu 9, E-28040 Madrid, Spain
3
International Institute Zittau (IHIZ), Technische Universität Dresden, Markt 23, D-02763 Zitau, Germany
*
Authors to whom correspondence should be addressed.
Academic Editor: Stanley Omaye
Antioxidants 2021, 10(12), 1888; https://doi.org/10.3390/antiox10121888
Received: 19 October 2021 / Revised: 20 November 2021 / Accepted: 25 November 2021 / Published: 25 November 2021
(This article belongs to the Special Issue Dream Peroxygenases)
Epoxide metabolites from n-3 and n-6 polyunsaturated fatty acids arouse interest thanks to their physiological and pharmacological activities. Their chemical synthesis has significant drawbacks, and enzymes emerge as an alternative with potentially higher selectivity and greener nature. Conversion of eleven eicosanoid, docosanoid, and other n-3/n-6 fatty acids into mono-epoxides by fungal unspecific peroxygenases (UPOs) is investigated, with emphasis on the Agrocybe aegerita (AaeUPO) and Collariella virescens (rCviUPO) enzymes. GC-MS revealed the strict regioselectivity of the n-3 and n-6 reactions with AaeUPO and rCviUPO, respectively, yielding 91%-quantitative conversion into mono-epoxides at the last double bond. Then, six of these mono-epoxides were obtained at mg-scale, purified and further structurally characterized by 1H, 13C and HMBC NMR. Moreover, chiral HPLC showed that the n-3 epoxides were also formed (by AaeUPO) with total S/R enantioselectivity (ee > 99%) while the n-6 epoxides (from rCviUPO reactions) were formed in nearly racemic mixtures. The high regio- and enantioselectivity of several of these reactions unveils the synthetic utility of fungal peroxygenases in fatty acid epoxidation. View Full-Text
Keywords: unspecific peroxygenases; epoxylipids; polyunsaturated fatty acids; omega 3 (n-3) fatty acids; omega 6 (n-6) fatty acids; bioactive compounds; regioselective synthesis; stereoselective synthesis; NMR; chiral HPLC unspecific peroxygenases; epoxylipids; polyunsaturated fatty acids; omega 3 (n-3) fatty acids; omega 6 (n-6) fatty acids; bioactive compounds; regioselective synthesis; stereoselective synthesis; NMR; chiral HPLC
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MDPI and ACS Style

González-Benjumea, A.; Linde, D.; Carro, J.; Ullrich, R.; Hofrichter, M.; Martínez, A.T.; Gutiérrez, A. Regioselective and Stereoselective Epoxidation of n-3 and n-6 Fatty Acids by Fungal Peroxygenases. Antioxidants 2021, 10, 1888. https://doi.org/10.3390/antiox10121888

AMA Style

González-Benjumea A, Linde D, Carro J, Ullrich R, Hofrichter M, Martínez AT, Gutiérrez A. Regioselective and Stereoselective Epoxidation of n-3 and n-6 Fatty Acids by Fungal Peroxygenases. Antioxidants. 2021; 10(12):1888. https://doi.org/10.3390/antiox10121888

Chicago/Turabian Style

González-Benjumea, Alejandro, Dolores Linde, Juan Carro, René Ullrich, Martin Hofrichter, Angel T. Martínez, and Ana Gutiérrez. 2021. "Regioselective and Stereoselective Epoxidation of n-3 and n-6 Fatty Acids by Fungal Peroxygenases" Antioxidants 10, no. 12: 1888. https://doi.org/10.3390/antiox10121888

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