Journal
BIOCHEMISTRY
Volume 57, Issue 13, Pages 1997-2008Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.biochem.8b00169
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Funding
- UK Catalysis Hub
- EPSRC [EP/K014706/1, EP/K014668/1, EP/K014854/1EP/K014714/1, EP/M022609/1, EP/M013219/1]
- BBSRC [BB/L018756/1, BB/M017702/1] Funding Source: UKRI
- EPSRC [EP/K014714/1, EP/J010588/1, EP/K014854/1] Funding Source: UKRI
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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. Phil (CHMOphil) 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 CHMOphil. 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 CCHMOphil, 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.
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