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Biocatalytic Routes to Lactone Monomers for Polymer Production

DOI: 10.1021/acs.biochem.8b00169 DOI Help

Authors: Hanan L. Messiha (University of Manchester) , Syed T. Ahmed (University of Manchester) , Vijaykumar Karuppiah (University of Manchester) , Reynier Suardiaz (University of Bristol) , Gabriel A. Ascue Avalos (University of Manchester) , Natalie Fey (University of Bristol) , Stephen Yeates (University of Manchester) , Helen S. Toogood (University of Manchester) , Adrian J. Mulholland (University of Bristol) , Nigel S. Scrutton (University of Manchester)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Biochemistry

State: Published (Approved)
Published: March 2018
Diamond Proposal Number(s): 12788

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.

Journal Keywords: Baeyer-Villiger monooxygenases (BVMOs); biocatalysis; crystallography; molecular dynamics simulations; DFT mechanistic study; biopolymers; ring-opening polymerization

Subject Areas: Chemistry, Biology and Bio-materials, Environment

Instruments: I03-Macromolecular Crystallography , I04-1-Macromolecular Crystallography (fixed wavelength)