6ER9

Crystal structure of cyclohexanone monooxygenase from Rhodococcus sp. Phi1 bound to NADP+

Summary for 6ER9

• Entry DOI: 10.2210/pdb6er9/pdb
• Descriptor: Cyclohexanone monooxygenase, FLAVIN-ADENINE DINUCLEOTIDE, NADP NICOTINAMIDE-ADENINE-DINUCLEOTIDE PHOSPHATE, ... (4 entities in total)
• Functional Keywords: monooxygenase, rossmann fold, fad, nadp+, lactone, dihydrocarvone, flavoprotein
• Biological source: Rhodococcus sp. Phi1
• Total number of polymer chains: 2
• Total formula weight: 124937.33

Authors

Karuppiah, V.,Scrutton, N.S. (deposition date: 2017-10-17, release date: 2018-09-26, Last modification date: 2024-01-17)

Primary citation

Messiha, H.L.,Ahmed, S.T.,Karuppiah, V.,Suardiaz, R.,Ascue Avalos, G.A.,Fey, N.,Yeates, S.,Toogood, H.S.,Mulholland, A.J.,Scrutton, N.S.
Biocatalytic Routes to Lactone Monomers for Polymer Production.
Biochemistry, 57:1997-2008, 2018

PubMed 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 (CHMO) 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. 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 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.

PubMed: 29533655
DOI: 10.1021/acs.biochem.8b00169

Experimental method

X-RAY DIFFRACTION (2.37 Å)