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dc.contributor.authorAranda, Carmen
dc.contributor.authorMunicoy, Martí
dc.contributor.authorGuallar, Victor
dc.contributor.authorKiebist, Jan
dc.contributor.authorScheibner, Katrin
dc.contributor.authorUllrich, René
dc.contributor.authordel Río, José C.
dc.contributor.authorHofrichter, Martin
dc.contributor.authorMartinez, Angel T.
dc.contributor.authorGutierrez, Ana
dc.contributor.otherBarcelona Supercomputing Center
dc.date.accessioned2019-04-16T08:27:31Z
dc.date.available2019-04-16T08:27:31Z
dc.date.issued2019-02-26
dc.identifier.citationAranda, C. [et al.]. Selective synthesis of 4-hydroxyisophorone and 4-ketoisophorone by fungal peroxygenases. "Catalysis Science and Technology", 26 Febrer 2019, vol. 9, p. 1398-1405.
dc.identifier.issn2044-4753
dc.identifier.urihttp://hdl.handle.net/2117/131764
dc.description.abstractThe recently discovered unspecific peroxygenases (UPOs) from the ascomycetes Chaetomium globosum and Humicola insolens were capable of selectively hydroxylating isophorone to 4-hydroxyisophorone (4HIP) and 4-ketoisophorone (4KIP), which are substrates of interest for the pharmaceutical and flavor-and-fragrance sectors. The model UPO from the basidiomycete Agrocybe aegerita was less regioselective, forming 7-hydroxyisophorone (and 7-formylisophorone) in addition to 4HIP. However, it was the most stereoselective UPO yielding the S-enantiomer of 4HIP with 88% ee. Moreover, using H. insolens UPO full kinetic resolution of racemic HIP was obtained within only 15 min, with >75% recovery of the R-enantiomer. Surprisingly, the UPOs from two other basidiomycetes, Marasmius rotula and Coprinopsis cinerea, failed to transform isophorone. The different UPO selectivities were rationalized by computational simulations, in which isophorone and 4HIP were diffused into the enzymes using the adaptive PELE software, and the distances from heme-bound oxygen in H2O2-activated enzyme to different substrate atoms, and the corresponding binding energies were analyzed. Interestingly, for process upscaling, full conversion of 10 mM isophorone was achieved with H. insolens UPO within nine hours, with total turnover numbers up to 5500. These biocatalysts, which only require H2O2 for activation, may represent a novel, simple and environmentally-friendly route for the production of isophorone derivatives.
dc.description.sponsorshipThis work was supported by the EnzOx2 (H2020-BBI-PPP-2015-2-1-720297) EU-project, the AGL2014-53730-R (BIORENZYMERY) and CTQ2016-79138-R projects of the Spanish MINECO (co-financed by FEDER) and the CSIC (201740E071) project. Novozymes (Bagsvaerd, Denmark) is acknowledged for providing samples of rCciUPO and rHinUPO.
dc.format.extent8 p.
dc.language.isoeng
dc.publisherRoyal Society of Chemistry
dc.rightsAttribution-NonCommercial-NoDerivs 3.0 Spain
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/es/
dc.subjectÀrees temàtiques de la UPC::Enginyeria biomèdica
dc.subject.lcshMolecular biology
dc.subject.other4-hydroxyisophorone (4HIP)
dc.subject.otherBiocatalysts
dc.titleSelective synthesis of 4-hydroxyisophorone and 4-ketoisophorone by fungal peroxygenases
dc.typeArticle
dc.subject.lemacBiologia molecular
dc.identifier.doi10.1039/C8CY02114G
dc.description.peerreviewedPeer Reviewed
dc.relation.publisherversionhttps://pubs.rsc.org/en/content/articlelanding/2019/cy/c8cy02114g#!divAbstract
dc.rights.accessOpen Access
dc.description.versionPostprint (published version)
dc.relation.projectidinfo:eu-repo/grantAgreement/EC/H2020/720297/EU/New enzymatic oxidation%2Foxyfunctionalization technologies for added value bio-based products/EnzOx2
dc.relation.projectidinfo:eu-repo/grantAgreement/MINECO/PE2013-2016/AGL2014-53730-R
dc.relation.projectidinfo:eu-repo/grantAgreement/MINECO/PE2013-2016/CTQ2016-79138-R
upcommons.citation.publishedtrue
upcommons.citation.publicationNameCatalysis Science and Technology
upcommons.citation.volume9
upcommons.citation.startingPage1398
upcommons.citation.endingPage1405


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