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Research subjects

by Federico Cisnetti - 13 November 2012

All the versions of this article: English , français

Area of expertise : organic and organometallic chemistry, chemistry-biology interface

Research subjects

  • Metallocarbenes: synthetic methodologies.
  • Click chemistry (new catalysts, metallocarbene and biomolecule functionalisation).
  • Anti-cancer platinum chelates, and coinage metal (Cu, Ag, Au) metallocarbenes.
  • Click lanthanide chelates : luminescence studies, lanthanide complexes-protein interaction. Inclusion in nanoparticles for medical imaging.
  • Biological activity of metallocarbenes: anticancer and antibacterial

Our research projects rely on efficient chemistry. Organometallic and coordination complexes are synthesized in straightforward and modular fashions in order to study them in the biological context. On the one hand, the biological activity of these compounds is determined. On the other hands, they are considered as catalysts - including for biomolecule functionalisation - or as luminescent probes for imaging applications.

All of the above-mentioned project rely on the so-called "click chemistry" approach. We develop highly efficient systems to perfom copper-catalysed azide-alkyne cycloadditions (CuAAC) at low catalyst loading. The triazole heterocycle such obtained is at the heart of the molecular system of biological interest. For instance, triazoles may participate to platinum chelation to yield cisplatin analogues, may play the role of antennae in sensitized luminescence of lanthanide complexes and expand their possibilities of intermolecular interaction with proteins or may introduce a functionalisation site distant to the carbenic core in metal N-heterocyclic carbenes (NHC) for solubility modulation and biomolecule conjugation.

Research highlights

Chemical Communications, 2014: ((Cu(IPr)2(μ-OH))(BF4): synthesis and halide-free CuAAC catalysis . The preparation under protic conditions of the first μ-hydroxo dicopper(I)–NHC complex is reported. Its application as a CuAAC catalyst was investigated, evidencing a remarkable enhancement of catalytic efficiency in the presence of 4,7-dichloro-1,10-phenanthroline and highlighting the beneficial effect of the absence of coordinating halides.

ChemMedChem, 2014: High-Throughput Screening of Metal-N-Heterocyclic Carbene Complexes against Biofilm Formation by Pathogenic Bacteria. A set of molecules including a majority of metal-N-heterocyclic carbene (NHC) complexes (metal=Ag, Cu, and Au) and azolium salts were evaluated by high-throughput screening of their activity against biofilm formation associated with pathogenic bacteria. This research was performed in collaboration with the universities of Strasbourg and Paris VI as well as the Biofilm Control company.

Organometallics, 2013: Simplified Preparation of Copper(I) NHCs Using Aqueous Ammonia. The use of aqueous ammonia as a coordinating and basic reagent for the metalation of imidazol(in)ium salts derived from (S)IPr and (S)IMes with simple inorganic copper precursors is reported. The synthesis of copper carbene complexes was performed using aqueous/alcoholic media in mild conditions (room temperature to 60 °C) with short reaction times.

Organometallics, 2012:CuAAC functionalization of azide-tagged copper(I)-NHCs acting as catalyst and substrate. We have developer copper(I) NHC complexes bearing azide functions. These species are able to act both as catalyst and substrate ad provide an original entry to functionalised metallocarbenes. This article is included in the Organometallics speial issue « Copper Organometallic Chemistry»

Chemical Communications, 2012: A Water Soluble CuI–NHC for CuAAC ligation of unprotected peptides under open air conditions. Using water-soluble copper(I)-NHC, CuAAC functionalisation of oligopeptides was efficiently performed in buffered aqueous media, in the presence of air without any sacrificial reducing agent. This study was performed in collaboration with Agnès Delmas and Vincent Aucagne from Molecular Biophysics Centre of Orléans.

ChemMedChem, 2012: Anticancer Activity of Silver–N-Heterocyclic Carbenes Complexes: Caspase-Independent Induction of Apoptosis via the Mitochondrial Apoptosis Inducing Factor (AIF). The unprecedented mechanim of action of silver(I)-NHCs against cancer cells was recently elucidated. Induction of apoptosis proved to follow an original pathway These study was performed in collaboration with Sylvain Roland (Parisian Institute of Molecular Chemistry), Thierry Cresteil (Institute of Chemistry of Natural Substances, Gif-sur-Yvette) the GReD laboratory as was as the Charles Friedel Laboratory of the National Superior School of Chemistry of Paris.

Chem Commun, 2012: Clicked europium dipicolinate complexes for protein X-ray structure determination . Novel trisdipicolinate-lanthanide complexes with triazole groups obtained by CuAAC are reported. Their use as phasing agents for accurate X-ray crystallographic structural determination of proteins is descibed. The CuAAC modification allows efficient protein co-crystallization with significantly lower concentration of lanthanide complexes in comparison to unmodified analogues.