Metal Ion Promiscuity and Structure of 2, 3‐Dihydroxybenzoic Acid Decarboxylase of Aspergillus oryzae. (23rd November 2020)

• Record Type: Journal Article
• Authors: Hofer, Gerhard; Sheng, Xiang; Braeuer, Simone; Payer, Stefan E.; Plasch, Katharina; Goessler, Walter; Faber, Kurt; Keller, Walter; Himo, Fahmi; Glueck, Silvia M.
• Is Part Of: Chembiochem. Volume 22:Number 4(2021)
• Page Start: 652
• Page End: 656
• Publication Date: 2020-11-23
• Subjects: biocatalysis -- computational chemistry -- enzyme structure -- metal-identity -- ortho-benzoic acid decarboxylase; Biochemistry -- Periodicals; Molecular biology -- Periodicals; Pharmaceutical chemistry -- Periodicals; 572
• DOI: 10.1002/cbic.202000600
• Languages: English
• ISSNs: 1439-4227

Abstract

Abstract: Broad substrate tolerance and excellent regioselectivity, as well as independence from sensitive cofactors have established benzoic acid decarboxylases from microbial sources as efficient biocatalysts. Robustness under process conditions makes them particularly attractive for preparative‐scale applications. The divalent metal‐dependent enzymes are capable of catalyzing the reversible non‐oxidative (de)carboxylation of a variety of electron‐rich (hetero)aromatic substrates analogously to the chemical Kolbe‐Schmitt reaction. Elemental mass spectrometry supported by crystal structure elucidation and quantum chemical calculations verified the presence of a catalytically relevant Mg 2+ complexed in the active site of 2, 3‐dihydroxybenoic acid decarboxylase from Aspergillus oryzae (2, 3‐DHBD_ Ao ). This unique example with respect to the nature of the metal is in contrast to mechanistically related decarboxylases, which generally have Zn 2+ or Mn 2+ as the catalytically active metal. Abstract : On your metal : Elucidation of the unique Mg 2+ ‐dependency of 2, 3‐dihydroxybenzoic acid decarboxylase from Aspergillus oryzae, a member of the amidohydroalse superfamily, facilitates a better structure‐activity prediction of the potential biocatalyst, which is capable of catalyzing the regioselective ortho ‐(de)carboxylation of phenol derivatives.