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Natural variation in the ‘control loop’ of BVMOAFL210 and its influence on regioselectivity and sulfoxidation

DOI: 10.3390/catal10030339 DOI Help

Authors: Carmien Tolmie (University of the Free State) , Rodolpho Do Aido-Machado (University of the Free State) , Felix Martin Ferroni (University of the Free State; Universidad Nacional del Litoral/CONICET) , Martha Sophia Smit (University of the Free State) , Diederik Johannes Opperman (Department of Biotechnology, University of the Free State)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Catalysts , VOL 10

State: Published (Approved)
Published: March 2020
Diamond Proposal Number(s): 18938

Open Access Open Access

Abstract: Baeyer-Villiger monooxygenases (BVMOs) are flavin-dependent enzymes that primarily convert ketones to esters, but can also catalyze heteroatom oxidation. Several structural studies have highlighted the importance of the ‘control loop’ in BVMOs, which adopts different conformations during catalysis. Central to the ‘control loop’ is a conserved tryptophan that has been implicated in NADP(H) binding. BVMOAFL210 from Aspergillus flavus, however, contains a threonine in the equivalent position. Here, we report the structure of BVMOAFL210 in complex with NADP+ in both the ‘open’ and ‘closed’ conformations. In neither conformation does Thr513 contact the NADP+. Although mutagenesis of Thr513 did not significantly alter the substrate scope, changes in peroxyflavin stability and reaction rates were observed. Mutation of this position also brought about changes in the regio- and enantioselectivity of the enzyme. Moreover, lower rates of overoxidation during sulfoxidation of thioanisole were also observed.

Journal Keywords: Baeyer-Villiger monooxygenase; lactone; ester; regioselectivity

Diamond Keywords: Enzymes

Subject Areas: Chemistry, Biology and Bio-materials

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

Added On: 08/04/2020 11:54


Discipline Tags:

Catalysis Life Sciences & Biotech Structural biology Chemistry Biochemistry

Technical Tags:

Diffraction Macromolecular Crystallography (MX)