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Polyether Cyclization Cascade Alterations in Response to Monensin Polyketide Synthase Mutations.
Heinrich, Sascha; Grote, Marius; Sievers, Sonja; Kushnir, Susanna; Schulz, Frank.
Afiliación
  • Heinrich S; Organic Chemistry I, Chemistry and Biochemistry of Natural Products, Ruhr-University Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
  • Grote M; Organic Chemistry I, Chemistry and Biochemistry of Natural Products, Ruhr-University Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
  • Sievers S; Max PIanck Institute for molecular Physiology, COMAS - Compound Management and Screening Center, Otto-Hahn-Straße 11, 44227, Dortmund, Germany.
  • Kushnir S; Organic Chemistry I, Chemistry and Biochemistry of Natural Products, Ruhr-University Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
  • Schulz F; Organic Chemistry I, Chemistry and Biochemistry of Natural Products, Ruhr-University Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
Chembiochem ; 23(2): e202100584, 2022 01 19.
Article en En | MEDLINE | ID: mdl-34729883
The targeted manipulation of polyketide synthases has in recent years led to numerous new-to-nature polyketides. For type I polyketide synthases the response of post-polyketide synthases (PKS) processing enzymes onto the most frequently polyketide backbone manipulations is so far insufficiently studied. In particular, complex processes such as the polyether cyclisation in the biosynthesis of ionophores such as monensin pose interesting objects of research. We present here a study of the substrate promiscuity of the polyether cyclisation cascade enzymes in monensin biosynthesis in the conversion of redox derivatives of the nascent polyketide chain. LC-HRMS/MS2 -based studies revealed a remarkable flexibility of the post-PKS enzymes. They acted on derivatized polyketide backbones based on the three possible polyketide redox states within two different modules and gave rise to an altered polyether structure. One of these monensin derivatives was isolated and characterized by 2D-NMR spectroscopy, crystallography, and bioactivity studies.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Monensina / Mutación Puntual / Sintasas Poliquetidas / Éteres Idioma: En Revista: Chembiochem Asunto de la revista: BIOQUIMICA Año: 2022 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Alemania

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Monensina / Mutación Puntual / Sintasas Poliquetidas / Éteres Idioma: En Revista: Chembiochem Asunto de la revista: BIOQUIMICA Año: 2022 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Alemania