Biocatalytic Routes to Lactone Monomers for Polymer Production

Hanan Messiha, Syed Ahmed, Vijaykumar Karuppiah, Reynier Suardiaz, Gabriel Ascue Avalos, Natalie Fey, Stephen Yeates, Helen Toogood, Adrian J. Mulholland, Nigel Scrutton

    Research output: Contribution to journalArticlepeer-review

    137 Downloads (Pure)

    Abstract

    Monoterpenoids offer potential as bio-derived monomer feedstocks for high performance renewable polymers. We describe a biocatalytic route to lactone monomers menthide and dihydrocarvide employing Baeyer-Villiger monooxygenases (BVMOs) from Pseudomonas sp. HI-70 (CPDMO) and Rhodococcus sp. Phi1 (CHMOPhi1) as an alternative to organic synthesis. The regio-selectivity of dihydrocarvide isomer formation was controlled by site-directed mutagenesis of three key active site residues in CHMOPhi1. A combination of crystal structure determination, molecular dynamics simulations and mechanistic modeling using density functional theory (DFT) on a range of models provides insight into the origins of discrimination of wild type (WT) and a variant CHMOPhi1 for producing different regio-isomers of the lactone product. Ring-opening polymerizations of the resultant lactones using mild metal-organic catalysts demonstrate their utility in polymer production. This semi-synthetic approach utilizing a biocatalytic step, non-petroleum feedstocks and mild polymerization catalysts, allows access to known and also to previously unreported and potentially novel lactone monomers and polymers.
    Original languageEnglish
    JournalBiochemistry
    Early online date13 Mar 2018
    DOIs
    Publication statusPublished - 2018

    Keywords

    • Baeyer-Villiger monooxygenases (BVMOs)
    • biocatalysis
    • Crystallography
    • Molecular dynamics simulations
    • DFT mechanistic study
    • biopolymers
    • Ring-opening polymerization

    Research Beacons, Institutes and Platforms

    • Manchester Institute of Biotechnology

    Fingerprint

    Dive into the research topics of 'Biocatalytic Routes to Lactone Monomers for Polymer Production'. Together they form a unique fingerprint.

    Cite this