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dc.contributor.author | Municoy, Martí | es_ES |
dc.contributor.author | González-Benjumea, Alejandro | es_ES |
dc.contributor.author | Carro, Juan | es_ES |
dc.contributor.author | Aranda, Carmen | es_ES |
dc.contributor.author | Linde, Dolores | es_ES |
dc.contributor.author | Renau-Mínguez, Chantal | es_ES |
dc.contributor.author | Hofrichter, Martin | es_ES |
dc.contributor.author | Guallar, Victor | es_ES |
dc.contributor.author | Gutiérrez Suárez, Ana | es_ES |
dc.contributor.author | Martínez, Ángel T. | es_ES |
dc.date.accessioned | 2020-12-04T12:08:38Z | - |
dc.date.available | 2020-12-04T12:08:38Z | - |
dc.date.issued | 2020-11-10 | - |
dc.identifier.citation | ACS Catalysis (10) 13584-13595 (2020) | es_ES |
dc.identifier.issn | 2155-5435 | - |
dc.identifier.uri | http://hdl.handle.net/10261/224429 | - |
dc.description | 12 páginas.- 6 figuras.- 1 tabla.- 84 referencias.- The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.0c03165 | es_ES |
dc.description.abstract | Epoxidation of unsaturated fatty acids by unspecific peroxygenases (UPOs) of the best-known long-UPO subfamily, including the Agrocybe aegerita (AaeUPO) and Coprinopsis cinerea enzymes, is reported here. To understand the different oxygenation patterns by members of the long-UPO and short-UPO subfamilies, the latter represented by the Marasmius rotula enzyme (MroUPO), fatty-acid diffusion into their heme pockets was simulated with the adaptive PELE software. Computational results shed light on the inability of AaeUPO to epoxidize oleic acid (C18:1), opposed to MroUPO, due to steric hindrances to harbor (with a good interaction energy) the substrate with the Δ9 C10 atom at a catalytically relevant distance (<3.5 Å) from the oxo group in simulated heme compound-I. However, effective α-linolenic acid epoxidation is anticipated because the Δ15 C16 atom would attain such a distance in AaeUPO thanks to its more terminal position. The above hypothesis was verified using an engineered MroUPO variant (I153F/S156F) with a narrowed heme access channel mimicking that of AaeUPO. Experimental oxygenation of unsaturated fatty acids by this variant thus resembles that of AaeUPO, including regioselective (from 95% to >99%) formation of cis,cis-15,16-epoxyoctadeca-9,12-dienoic acid. The nearly complete conversion of α-linolenic acid by the two enzymes was transferred to a small preparative scale, the yield of purified product was estimated, its chemical structure analyzed by NMR, and more interestingly, stereoselective production of the 15(R),16(S) enantiomer (80-83% ee) assessed by chiral HPLC. This enzymatic synthesis overcomes the unspecificity of chemical epoxidation where the reaction cannot be restricted to the formation of monoepoxides as found during m-perchlorobenzoic acid oxidation of α-linolenic acid. Moreover, the variant was able to produce the unsaturated dicarboxylic fatty acid, together with subterminal oxygenation products, during partial conversion of oleic acid. These two noteworthy reactions had not been reported for any UPO described to date. © 2020 American Chemical Society. All rights reserved. | es_ES |
dc.description.sponsorship | This work has received funding from the Bio Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation programme under Grant Agreement No 792063 (“Development and pilot production of sustainable binder systems for wood based panels”, https://susbind.eu ), the CTQ2016-79138-R and BIO2017-86559-R projects of Spanish MINECO, the Secretaria d’Universitats i Recerca of Generalitat de Catalunya, and the European Social Fund (ESF-2019-FI-B-00154). The authors thank Novozymes A/S for supplying r CciUPO. MM acknowledges a Catalan Government doctoral grant. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | American Chemical Society | es_ES |
dc.relation | info:eu-repo/grantAgreement/EC/H2020/792063 | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-79138-R | es_ES |
dc.relation | info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/BIO2017-86559-R | es_ES |
dc.relation | info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/ESF-2019-FI-B-00154 | es_ES |
dc.relation.isversionof | Publisher's version | es_ES |
dc.rights | openAccess | es_ES |
dc.subject | Adaptive-PELE | es_ES |
dc.subject | Computational chemistry | es_ES |
dc.subject | Fungal unspecific peroxygenases | es_ES |
dc.subject | Monte Carlo molecular simulations | es_ES |
dc.subject | Oxygenation patterns | es_ES |
dc.subject | Regioselective epoxidation | es_ES |
dc.subject | Stereoselective epoxidation | es_ES |
dc.subject | Unsaturated fatty acids | es_ES |
dc.title | Fatty-Acid Oxygenation by Fungal Peroxygenases: From Computational Simulations to Preparative Regio- and Stereoselective Epoxidation | es_ES |
dc.type | artículo | es_ES |
dc.identifier.doi | 10.1021/acscatal.0c03165 | - |
dc.description.peerreviewed | Peer reviewed | es_ES |
dc.relation.publisherversion | http://dx.doi.org/10.1021/acscatal.0c03165 | es_ES |
dc.rights.license | https://pubs.acs.org/page/policy/authorchoice_termsofuse.html | es_ES |
dc.contributor.funder | European Commission | es_ES |
dc.contributor.funder | Ministerio de Economía y Competitividad (España) | es_ES |
dc.contributor.funder | Generalitat de Catalunya | es_ES |
dc.relation.csic | Sí | es_ES |
oprm.item.hasRevision | no ko 0 false | * |
dc.identifier.funder | http://dx.doi.org/10.13039/501100000780 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100002809 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100003329 | es_ES |
dc.contributor.orcid | González-Benjumea, Alejandro [0000-0003-2857-9491] | es_ES |
dc.contributor.orcid | Carro, Juan [0000-0002-7556-9782] | es_ES |
dc.contributor.orcid | Aranda, Carmen [0000-0001-8213-1132] | es_ES |
dc.contributor.orcid | Renau-Mínguez, Chantal [0000-0003-1308-7013] | es_ES |
dc.contributor.orcid | Guallar, Victor [0000-0002-4580-1114] | es_ES |
dc.contributor.orcid | Gutiérrez Suárez, Ana [0000-0002-8823-9029] | es_ES |
dc.contributor.orcid | Martínez, Ángel T. [0000-0002-1584-2863] | es_ES |
dc.contributor.orcid | Hofrichter, Martin [0000-0001-5174-7604] | - |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.openairetype | artículo | - |
item.grantfulltext | open | - |
item.cerifentitytype | Publications | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.fulltext | With Fulltext | - |
item.languageiso639-1 | en | - |
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Fatty_Acid_oxygenation_fungal_2020.pdf | 6,49 MB | Adobe PDF | Visualizar/Abrir |
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