6f97
From Proteopedia
Crystal structure of the V465T mutant of 5-(Hydroxymethyl)furfural Oxidase (HMFO)
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 PubMedVarious 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
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