Biocatalytic Routes to Lactone Monomers for Polymer Production

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

Research output: Contribution to journalArticle (Academic Journal)peer-review

23 Citations (Scopus)
390 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
Pages (from-to)1997-2008
Number of pages12
JournalBiochemistry
Volume57
Issue number13
Early online date13 Mar 2018
DOIs
Publication statusPublished - 3 Apr 2018

Keywords

  • Baeyer-Villiger monooxygenases (BVMOs)
  • biocatalysis
  • crystallography
  • molecular dynamics simulations
  • DFT mechanistic study
  • biopolymers
  • ring-opening polymerization

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