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Emmanuel Tirel

  • PhD student
  • Group of Nick Williams
  • Department of Chemistry, Sheffield University, UK
  • Contact email: e.tirel (please add @sheffield.ac.uk)

Background: I studied biology and chemistry at the University of Savoie (Chambéry, France) and then moved to chemistry with two year of Master at University Joseph Fourier (Grenoble, France). I joined the laboratory of Dr. Stephane Menage (Chemistry and Biology of Metals, CEA Grenoble) to research bio-inspired reduction of N2O by sulfido mixed-valent copper catalyst for my Master thesis.

Training and Transferable Skills:
- ligand and complex synthesis (glove box)
- characterization (NMR, EPR, UV-vis spectroscopy, Mass spectroscopy, X-ray diffraction)
- kinetics

Research Projects: I am working on the development of zinc based catalyst for phosphodiester cleavage (DNA and RNA like substrate). Bio-mimetic hydrolysis of DNA (Fig. 1) or RNA is of increasing importance in biotechnology and medicine. The ability to cleave nucleic acids efficiently in a non-degradative manner and with high levels of site or structure selectivity will offer many applications for the manipulation of genes and the development of new therapies. Moreover the development of synthetic small metallonucleases would expand our comprehension of how enzymes catalyse the reaction and provide such an important acceleration (up to 1016).
A large part of the acceleration in theses metalloenzymes is provided by the metal itself. It have also been shown that its reactivity can be enhanced by key amino acid residues in close proximity. Following this concept, I am investigating the effect of the metal microenvironment (H-Bond, Fig. 2, and steric effect) on our catalyst.
Another focus of my project is the nucleophile itself. By structural modification, I am aiming to get more insight on how its properties (nucleophilicity, concentration, orientation) impact the reactivity.


emmanuelfig01

Figure 1: Hydrolysis of the DNA P-O Phosphodiester bond.


emmanuelfig02

Figure 2: Dinuclear Zinc catalyst bind to 4-nitrophenyl phosphate, zinc green, oxygen red, phosphorus yellow, nitrogen blue, H-bond light blue.