Institut de Chimie Moléculaire et des Matériaux d'Orsay

Laboratoire de Chimie Bioorganique et Bioinorganique - LCBB

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Subject 2 (J.-P. Mahy)
Design and synthesis of new metal complexes
and study of their interactions with biomolecules

R. Ricoux, F. Avenier, W. Ghattas, J.-P. Mahy



2.1. Artificial metalloenzymes for enantioselective oxidation catalysis

(xylanases, alpha-Rep, beta-lactoglobuline)
R. Ricoux



Artificial metalloenzymes, obtained by non-covalent insertion of Mn(III)-meso-tetrakis(para-carboxyphenyl)porphyrin, Mn(TpCPP), into xylanase 10A from Streptomyces lividans as a host protein were found to be able to catalyse the oxidation of para-methoxystyrene by KHSO5 with a 16% yield and the best enantioselectivity (80% in favour of the R isomer) ever reported for an artificial metalloenzyme.

ChemBioChem (2012) 13, 240-251. Chem. Commun. (2015) 51, 2476-2494



An artificial metalloenzyme has been prepared by covalent grafting of a non-heme Fe(II) complex into bovine β-lactoglobulin. This biohybrid catalyst activates H2O2 to oxidize thioanisole into phenylmethylsulfoxide as the sole product with an enantiomeric excess of up to 20 %. A high-spin (S = 5/2) Fe(II) m(η2-O2) intermediate was identified as the active species in the catalytic sulfoxidation of the substrate.

Chem. Eur. J. (2015), 21, 12188-12193