Abstract
Monoterpenoids offer potential as biocatalytically 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 regioselectivity 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 on a range of models provides insight into the origins of the discrimination of the wild type and a variant CHMOPhi1 for producing different regioisomers of the lactone product. Ring-opening polymerizations of the resultant lactones using mild metal-organic catalysts demonstrate their utility in polymer production. This semisynthetic 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 language | English |
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Pages (from-to) | 1997-2008 |
Number of pages | 12 |
Journal | Biochemistry |
Volume | 57 |
Issue number | 13 |
Early online date | 13 Mar 2018 |
DOIs | |
Publication status | Published - 3 Apr 2018 |
Keywords
- RCUK
- BBSRC
- EPSRC
- EP/K014706/1
- EP/K014668/1
- EP/K014854/1
- EP/ K014714/1
- EP/M022609/1
- EP/M013219/1