Published on 23 July 2019
Research
Aerobic Baeyer–Villiger Oxidation Catalyzed by a Flavin‐Containing Enzyme Mimic in Water

During IUPAC 2019 congress, which took place from 7 to 12 July in Paris, Frédéric Avenier, researcher at Orsay Institute of Molecular Chemistry and Materials (ICMMO - CNRS/Université Paris-Sud), showed some of his research work on the development of artificial enzymes to carry out new chemical reactions catalysed in aqueous solution.

Flavoenzymes are ubiquitous biocatalysts: present in all cells, they are essential intermediates for metabolic pathways (degradation or transformation of components in cells). Their particularity is that they have the same subunit, a cofactor that is a derivative of flavine. However, depending on the proteins, this cofactor has different roles: it can either activate oxygen to carry out oxidation or be a partner for electron transport and donation.

Transposing chemical reactions carried out by enzymes to the laboratory is a major challenge: most of them are often only soluble in water and and their three-dimensionality active site is essential for reactions. However, finding inspiration in Nature is still possible.

This is what Frédéric Avenier's team at Orsay Institute of Molecular Chemistry and Materials did. Using a flavine-based cofactor and a water-soluble polymer, the researchers created a locally hydrophobic microenvironment to host the substrates for chemical reactions. From this artificial enzyme and in the presence of other reaction partners, they recreated the same conditions necessary for reactivity as that of the natural enzyme. Their goal: to carry out oxidation-reduction reactions using the oxygen in the air while working in water.

Where the enzyme was limited to the substrates present in the cell, the artificial enzyme has a much broader reactivity spectrum: it reacts with highly hydrophobic or poorly compatible reagents with living organisms.

Through this work, the ICMMO team shows that it is possible to imitate Nature while respecting the environment. The researchers are continuing their project to improve already very encouraging yields, with an industrial-scale development objective.

 

Aerobic Baeyer-Villiger Oxidation Catalyzed by a Flavin-Containing Enzyme Mimic in Water. Y. Chevalier, Y. Lock Toy Ki,  D. le Nouen,  J.-P. Mahy,  J.-P. Goddard, F. Avenier. Angew. Chem. Int. Ed. 2018, 57, 16412-16415

Bio-inspired electron-delivering system for reductive activation of dioxygen at metal centres towards artificial flavoenzymesY.Roux, R. Ricoux, F. Avenier, J.-P. Mahy. Nature Commun. 2015, 6, 8509.