Marie Skłodowska-Curie Actions - Individual Fellowship
BiomCatOx is an academic research project funded by the European Commission within Horizon 2020.
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BiomCatOx explores a unique catalyst design for the valorisation of hydrocarbons by oxygen insertion into a C–H bond under mild reaction conditions and using O2 as cheap and benign oxidant. The key concept of BiomCatOx is to rigorously control the activation of O2 and the formation of metal-based reactive oxygen species (ROS) to accomplish selective and catalytic oxidation of hydrocarbons. The novelty of BiomCatOx lies in the design of the catalyst that consists in connecting a metallo-peptide as electron relay for controllable intramolecular electron transfer (IET) to a synthetic oxidation catalyst. The intramolecular electron transfer can be rationally custom-tailored and therefore provides strict control on the reactivity of the catalytic center and on the formation of the ROS. BiomCatOx uses a stepwise approach involving (i) the development of copper-NHC complexes as powerful catalysts for the formation of ROS and hydrocarbon oxidation, (ii) the development of a copper peptide derived from the azurin active site for efficient electron transfer, and (iii) the covalent connection of the two copper sites into a peptide-complex dicopper conjugate for controlled intramolecular electron transfer. The implementation of BiomCatOx will provide efficient catalytic systems and fundamental insights into electron transfer, and discloses a new catalyst design concept. BiomCatOx is highly interdisciplinary and merges organometallic chemistry, homogeneous catalysis, enzymology, and spectroscopy.
Media Corner
Euresearch "Success Story"
Crossing Borders to Nurture Excellence
March 2019
Euresearch, a swiss association, focuses on informing, advising and connecting researchers in Switzerland. Through their "Success Stories", Euresearch highlights research excellence in Switzerland. A portrait of our innovative project and the future opportunities the H2020 program offers has been drawn.
Scientific productions
The scientific outputs were gathered and published in high-impact peer-reviewed journals.
Carbene in Cupredoxin Protein Scaffolds: Replacement of a Histidine Ligand in the Active Site Substantially Alters Copper Redox Properties
27 June 2018
N-heterocyclic carbene (NHC) ligands have had a major impact in homogeneous catalysis, however, their potential role in biological systems is essentially unexplored. We replaced a copper-coordinating histidine (His) in the active site of the redox enzyme azurin with exogenous dimethyl imidazolylidene. This NHC rapidly restores the type-1 Cu center, with spectroscopic properties (EPR, UV/Vis) that are identical to those from N-coordination of the His in the wild type. However, the introduction of the NHC markedly alters the redox potential of the metal, which is a key functionality of this blue copper protein. These suggest that C-bonding for histidine is plausible and a potentially relevant bonding mode of redox-active metalloenzymes in their (transient) active states.
Imidazolylidene Cu(II) Complexes: Synthesis Using Imidazolium Carboxylate Precursors and Structure Rearrangement Pathways
12 November 2019
Copper(II) complexes of type (NHC)CuX2 (X = OAc, Cl, Br, BF4, and NO3) bearing monodentate N- heterocyclic carbenes (NHCs) were prepared by in situ decarboxylation of imidazolium carboxylates as a new synthetic methodology for Cu(II)-NHC complexes. In contrast to the classical deprotonation method, the decarboxylation protocol does not require anaerobic conditions and provides access to complexes with NHCs that are unstable as free carbenes such as N,N′- diisopropyl-imidazolylidene and N,N′-dimethyl-imidazolylidene. Spectroscopic evidence of the formation of the Cu−CNHC bond is provided by UV−vis and EPR, in particular by the 44 MHz carbene hyperfine coupling constant using a 13C-labeled imidazolylidene ligand. A variation of the nature of the carbene N-substituents and the anions bound to the Cu(II) center is possible with this methodology. These variations strongly influence the stability of the complexes. Structural rearrangement and ligand reorganization was observed during recrystallization, which are comprised of heterolytic Cu−CNHC bond dissociation for unstable NHC ligands as well as homolytic Cu−X bond cleavage and disproportionation reactions depending on the nature of the anion X in the copper complex.
Workshops
Euresearch workshop
MSC IF proposal preparation
June 2018
Euresearch, a swiss association, offers trainings and workshops to increase the excellence of research proposals in the grant applications process. In order to share my experience with MSC Individual Fellowship application, I have been invited to exchange on the preparation of such an application, focusing on the writing stage.
Albrecht Research Group
Departement for Chemistry and Biochemistry
University of Berne, Switzerland
