Institut Parisien de Chimie Moléculaire

http://orcid.org/0000-0003-3039-5659

Research interests:

bioorganometallic chemistry

Current research:

• Theme 1 : Design of artificial metalloenzymes for asymmetric catalysis in aqueous medium
• Theme 2 : Medicinal organometallic chemistry

Recent results:

• Theme 1 : Artificial metalloenzymes (ArMs)

We have designed and prepared artificial metalloproteins for asymmetric transfer hydrogenation of aromatic ketones. These ArMs were built up by covalent, supramolecular or dative anchoring of Ru- or Rh-based synthetic metal cofactors to papain or bovine beta-lactoglobulin. The X-ray structure of an ArM derived from b-LG shows an insertion of the metal cofactor in the central cavity of b-LG. Transfer hydrogenation of trifluoroacetophenone was achieved with an enantiomeric excess of 32% (R). A more efficient ArM was built up by dative anchoring of an half-sandwich Ru complex to b-LG. This ArM catalysed the transfer hydrogenation of trifluoroacetophenone in 93% yield and 87% enantiomeric excess (R).

• Theme 2 : Medicinal organometallic chemistry
  We developed an array of half-sandwich iridium(III) complexes comprising a phenylpyridine or phenyloxazoline chelating ligand with cytotoxic activity of cancer cell lines. A BODIPY fluorescent probe was appended to the iridium complexes so as to measure the cell uptake rate and subcellular distribution by fluorescence microscopy. Studies are ongoing to get insight into the mechanism of action of these molecules.

Scientific career

• 1987 : Engineer graduated from the Ecole Nationale Superieure de Chimie de Paris
• 1987 : DEA in organic chemistry of the Université Pierre et Marie Curie
• 1990 : Ph. D. thesis in organic chemistry, Université Pierre et Marie Curie under the supervision of Professor Gerard Jaouen. Title of the thesis : synthesis of metal carbonyl derivatives of pharmaceutical drugs ; application to the immunological assay of haptens by Fourier transform infrared
• 2001 : Coordination chemistry division of the French chemical society award
• 2005 : Habilitation delivered by the Université Pierre et Marie Curie
• 1991 : Post-doctoral studies financed by CNRS and Medgenx company
• 1992 – 2008 : chargée de recherche CNRS
• depuis 2008 : directrice de recherche CNRS

Selected publications:

Thème 1

1. A. Chevalley, and M. Salmain. (2012) Enantioselective transfer hydrogenation of ketone catalysed by artificial metalloenzymes derived from bovine b-lactoglobulin, Chem. Commun. 48, 11984-11986; doi: 10.1039/c2cc36980j.
2. M. V. Cherrier, S. Engilberge, P. Amara, A. Chevalley, M. Salmain, and J. C. Fontecilla-Camps. (2013) Structural basis for enantioselectivity in the transfer hydrogenation of a ketone catalyzed by an artificial metalloenzyme, Eur. J. Inorg. Chem., 3596-3600; doi: 10.1002/ejic.201300592.
3. A. Chevalley, M. V. Cherrier, J. C. Fontecilla-Camps, M. Ghasemi, and M. Salmain. (2014) Artificial metalloenzymes derived from bovine β-lactoglobulin for the asymmetric transfer hydrogenation of an aryl ketone – synthesis, characterization and catalytic activity, Dalton Trans. 43, 5482 – 5489 ; doi : 10.1039/c3dt53253d.
4. Cazares-Marinero, J. de J.; Przybylski, C.; Salmain, M. Proteins as Macromolecular Ligands for Metal-Catalysed Asymmetric Transfer Hydrogenation of Ketones in Aqueous Medium. Eur. J. Inorg. Chem. 2018, 1383–1393, doi:10.1002/ejic.201701359.

Thème 2

1. Zimbron, J.M.; Passador, K.; Gatin-Fraudet, B.; Bachelet, C.-M.; Plazuk, D.; Chamoreau, L.-M.; Botuha, C.; Thorimbert, S.; Salmain, M. Synthesis, Photophysical Properties, and Living Cell Imaging of Theranostic Half-Sandwich Iridium-4,4-Difluoro-4-Bora-3a,4a-Diaza-s-Indacene (BODIPY) Dyads. Organometallics 2017, 36, 3435–3442, doi:10.1021/acs.organomet.7b00250.
2. Ramos, R.; Zimbron, J.M.; Thorimbert, S.; Chamoreau, L.-M.; Munier, A.; Botuha, C.; Karaiskou, A.; Salmain, M.; Sobczak-Thépot, J. Insights into the Antiproliferative Mechanism of (C^N)-Chelated Half-Sandwich Iridium Complexes. Dalton Trans. 2020, 49, 17635–17641, doi:10.1039/D0DT03414B.
3. Ramos, R.; Gilles, J.-F.; Morichon, R.; Przybylski, C.; Caron, B.; Botuha, C.; Karaiskou, A.; Salmain, M.; Sobczak-Thépot, J. Cytotoxic BODIPY-Appended Half-Sandwich Iridium(III) Complex Forms Protein Adducts and Induces ER Stress. J. Med. Chem. 2021, 64, 16675–16686, doi:10.1021/acs.jmedchem.1c01335.