Structural highlights
Function
[HMFO_METS6] Involved in the degradation and detoxification of 5-(hydroxymethyl)furfural (HMF) by mediating its oxidation to furan-2,5-dicarboxylate (FDCA), a biobased platform chemical for the production of polymers. Active with a wide range of aromatic and aliphatic primary alcohols and aldehydes: acts on alcohol groups and requires the spontaneous hydration of aldehyde groups for their oxidation (PubMed:24271187, PubMed:24802551). To a lesser extent, is also able to catalyze the oxidation of thiols that are structurally similar to its alcohol substrates, yielding the corresponding thiocarbonyls (PubMed:25284255).[1] [2] [3]
Publication Abstract from PubMed
Various flavoprotein oxidases were recently shown to oxidize prim-thiols. Here we extend this reactivity towards sec-thiols via structure-guided engineering of 5-(hydroxymethyl)furfural oxidase (HMFO). The variants obtained were employed for the oxidative kinetic resolution of rac-sec-thiols yielding the correspon notding thioketones and nonreacted (R)-thiols with excellent enantioselectivities (E >/= 200). The engineering strategy applied went beyond the classic approach of replacing bulky amino acid residues with smaller ones, as the active site was additionally enlarged by a newly introduced Thr residue that establishes a hydrogen bonding interaction with the substrates, as predicted by modelling and verified in the crystal structure of the variant. These strategies unlocked HMFO variants for the enantioselective oxidation of a range of sec-thiols.
Kinetic Resolution of sec-Thiols via Enantioselective Oxidation with Rationally Engineered 5-(Hydroxymethyl)furfural Oxidase.,Pickl M, Swoboda A, Romero E, Winkler C, Binda C, Mattevi A, Faber K, Fraaije M Angew Chem Int Ed Engl. 2018 Jan 31. doi: 10.1002/anie.201713189. PMID:29384246[4]
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine.
References
- ↑ Dijkman WP, Fraaije MW. Discovery and characterization of a 5-hydroxymethylfurfural oxidase from Methylovorus sp. strain MP688. Appl Environ Microbiol. 2014 Feb;80(3):1082-90. doi: 10.1128/AEM.03740-13. Epub, 2013 Nov 22. PMID:24271187 doi:http://dx.doi.org/10.1128/AEM.03740-13
- ↑ Dijkman WP, Groothuis DE, Fraaije MW. Enzyme-catalyzed oxidation of 5-hydroxymethylfurfural to furan-2,5-dicarboxylic acid. Angew Chem Int Ed Engl. 2014 Jun 16;53(25):6515-8. doi: 10.1002/anie.201402904., Epub 2014 May 6. PMID:24802551 doi:http://dx.doi.org/10.1002/anie.201402904
- ↑ Ewing TA, Dijkman WP, Vervoort JM, Fraaije MW, van Berkel WJ. The oxidation of thiols by flavoprotein oxidases: a biocatalytic route to reactive thiocarbonyls. Angew Chem Int Ed Engl. 2014 Nov 24;53(48):13206-9. doi: 10.1002/anie.201407520. , Epub 2014 Oct 5. PMID:25284255 doi:http://dx.doi.org/10.1002/anie.201407520
- ↑ Pickl M, Swoboda A, Romero E, Winkler C, Binda C, Mattevi A, Faber K, Fraaije M. Kinetic Resolution of sec-Thiols via Enantioselective Oxidation with Rationally Engineered 5-(Hydroxymethyl)furfural Oxidase. Angew Chem Int Ed Engl. 2018 Jan 31. doi: 10.1002/anie.201713189. PMID:29384246 doi:http://dx.doi.org/10.1002/anie.201713189
