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Publication - Professor Adrian Mulholland

    Biocatalytic Routes to Lactone Monomers for Polymer Production

    Citation

    Messiha, HL, Ahmed, ST, Karuppiah, V, Suardiaz, R, Avalos, GAA, Fey, N, Yeates, S, Toogood, HS, Mulholland, AJ & Scrutton, NS, 2018, ‘Biocatalytic Routes to Lactone Monomers for Polymer Production’. Biochemistry, vol 57., pp. 1997-2008

    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.

    Full details in the University publications repository