3 research outputs found

    Biocatalytic Routes to Lactone Monomers for Polymer Production

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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 <i>Pseudomonas</i> sp. HI-70 (CPDMO) and <i>Rhodococcus</i> sp. Phi1 (CHMO<sub>Phi1</sub>) 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 CHMO<sub>Phi1</sub>. 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 CHMO<sub>Phi1</sub> 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

    Biocatalytic Routes to Lactone Monomers for Polymer Production

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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 <i>Pseudomonas</i> sp. HI-70 (CPDMO) and <i>Rhodococcus</i> sp. Phi1 (CHMO<sub>Phi1</sub>) 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 CHMO<sub>Phi1</sub>. 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 CHMO<sub>Phi1</sub> 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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