Natural Variation in the ‘Control Loop’ of BVMOAFL210 and Its Influence on Regioselectivity and Sulfoxidation

Tolmie, Carmien; do Aido-Machado, Rodolpho; Ferroni, Felix Martin; Smit, Martha Sophia; Opperman, Diederik Johannes

doi:10.3390/catal10030339

Submit to this Journal Review for this Journal Edit a Special Issue

Article Menu

...

Open AccessArticle

Natural Variation in the ‘Control Loop’ of BVMO_AFL210 and Its Influence on Regioselectivity and Sulfoxidation

Carmien Tolmie

Rodolpho do Aido-Machado

Felix Martin Ferroni

^1,2

Martha Sophia Smit

¹ and

Diederik Johannes Opperman

^1,*

University of the Free State, Department of Biotechnology, Bloemfontein 9300, South Africa

Universidad Nacional del Litoral/CONICET, Departamento de Física, Santa Fe S3000ZAA, Argentina

Author to whom correspondence should be addressed.

Catalysts 2020, 10(3), 339; https://doi.org/10.3390/catal10030339

Received: 21 February 2020 / Revised: 9 March 2020 / Accepted: 9 March 2020 / Published: 19 March 2020

(This article belongs to the Special Issue Flavin Monooxygenases)

View Full-Text Download PDF

Browse Figures

Citation Export

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. BVMO_AFL210 from Aspergillus flavus, however, contains a threonine in the equivalent position. Here, we report the structure of BVMO_AFL210 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. View Full-Text

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

▼ Show Figures

Figure 1

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited

Supplementary Material

Supplementary File 1:
PDF-Document (PDF, 571 KiB)

Share and Cite

MDPI and ACS Style

Tolmie, C.; do Aido-Machado, R.; Ferroni, F.M.; Smit, M.S.; Opperman, D.J. Natural Variation in the ‘Control Loop’ of BVMO_AFL210 and Its Influence on Regioselectivity and Sulfoxidation. Catalysts 2020, 10, 339. https://doi.org/10.3390/catal10030339

AMA Style

Tolmie C, do Aido-Machado R, Ferroni FM, Smit MS, Opperman DJ. Natural Variation in the ‘Control Loop’ of BVMO_AFL210 and Its Influence on Regioselectivity and Sulfoxidation. Catalysts. 2020; 10(3):339. https://doi.org/10.3390/catal10030339

Chicago/Turabian Style

Tolmie, Carmien, Rodolpho do Aido-Machado, Felix M. Ferroni, Martha S. Smit, and Diederik J. Opperman. 2020. "Natural Variation in the ‘Control Loop’ of BVMO_AFL210 and Its Influence on Regioselectivity and Sulfoxidation" Catalysts 10, no. 3: 339. https://doi.org/10.3390/catal10030339

Find Other Styles

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Metrics

Abstract views Pdf views Html views

Article Menu

Natural Variation in the ‘Control Loop’ of BVMO_AFL210 and Its Influence on Regioselectivity and Sulfoxidation

Abstract

Supplementary Material

Share and Cite

Article Metrics

Article Access Statistics

Article Access Map by Country/Region

Further Information

Guidelines

MDPI Initiatives

Follow MDPI