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Mechanistic insights into glycoside 3-oxidases involved in C-glycoside metabolism in soil microorganisms.
Taborda, André; Frazão, Tomás; Rodrigues, Miguel V; Fernández-Luengo, Xavier; Sancho, Ferran; Lucas, Maria Fátima; Frazão, Carlos; Melo, Eduardo P; Ventura, M Rita; Masgrau, Laura; Borges, Patrícia T; Martins, Lígia O.
Afiliación
  • Taborda A; Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av da República, 2780-157, Oeiras, Portugal.
  • Frazão T; Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av da República, 2780-157, Oeiras, Portugal.
  • Rodrigues MV; Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av da República, 2780-157, Oeiras, Portugal.
  • Fernández-Luengo X; Department of Chemistry, Universitat Autònoma de Barcelona, 08193, Bellaterra, Spain.
  • Sancho F; Zymvol Biomodeling, C/ Pau Claris, 94, 3B, 08010, Barcelona, Spain.
  • Lucas MF; Zymvol Biomodeling, C/ Pau Claris, 94, 3B, 08010, Barcelona, Spain.
  • Frazão C; Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av da República, 2780-157, Oeiras, Portugal.
  • Melo EP; Centro de Ciências do Mar, Universidade do Algarve, 8005-139, Faro, Portugal.
  • Ventura MR; Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av da República, 2780-157, Oeiras, Portugal.
  • Masgrau L; Department of Chemistry, Universitat Autònoma de Barcelona, 08193, Bellaterra, Spain.
  • Borges PT; Zymvol Biomodeling, C/ Pau Claris, 94, 3B, 08010, Barcelona, Spain.
  • Martins LO; Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av da República, 2780-157, Oeiras, Portugal.
Nat Commun ; 14(1): 7289, 2023 11 14.
Article en En | MEDLINE | ID: mdl-37963862
C-glycosides are natural products with important biological activities but are recalcitrant to degradation. Glycoside 3-oxidases (G3Oxs) are recently identified bacterial flavo-oxidases from the glucose-methanol-coline (GMC) superfamily that catalyze the oxidation of C-glycosides with the concomitant reduction of O2 to H2O2. This oxidation is followed by C-C acid/base-assisted bond cleavage in two-step C-deglycosylation pathways. Soil and gut microorganisms have different oxidative enzymes, but the details of their catalytic mechanisms are largely unknown. Here, we report that PsG3Ox oxidizes at 50,000-fold higher specificity (kcat/Km) the glucose moiety of mangiferin to 3-keto-mangiferin than free D-glucose to 2-keto-glucose. Analysis of PsG3Ox X-ray crystal structures and PsG3Ox in complex with glucose and mangiferin, combined with mutagenesis and molecular dynamics simulations, reveal distinctive features in the topology surrounding the active site that favor catalytically competent conformational states suitable for recognition, stabilization, and oxidation of the glucose moiety of mangiferin. Furthermore, their distinction to pyranose 2-oxidases (P2Oxs) involved in wood decay and recycling is discussed from an evolutionary, structural, and functional viewpoint.
Asunto(s)

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Oxidorreductasas / Glicósidos Cardíacos Idioma: En Revista: Nat Commun Asunto de la revista: BIOLOGIA / CIENCIA Año: 2023 Tipo del documento: Article País de afiliación: Portugal Pais de publicación: Reino Unido

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Oxidorreductasas / Glicósidos Cardíacos Idioma: En Revista: Nat Commun Asunto de la revista: BIOLOGIA / CIENCIA Año: 2023 Tipo del documento: Article País de afiliación: Portugal Pais de publicación: Reino Unido