Poster Presentation 8th Modern Solid Phase Peptide Synthesis & Its Applications Symposium 2022

Photoaffinity labelling for the elucidation of mycocyclosin target protein(s) (#137)

Hannah Ryan 1 , Craig Hutton 1
  1. The University of Melbourne, Carlton, VIC, Australia

Today, tuberculosis remains one of the top 10 causes of death worldwide, and the leading cause from a single infectious agent – mycobacterium tuberculosis (Mtb).1 The gene encoding the Mtb enzyme CYP121 is essential for mycobacterial viability. 2 CYP121 catalyses the final step in the biosynthesis of mycocyclosin, a cross-linked cyclic dipeptide. 3 It is therefore postulated that mycocyclosin has a crucial role in Mtb viability – yet the biological role of this compound remains unknown.

We aim to elucidate the molecular target of mycocyclosin using a photoaffinity labelling (PAL) strategy, which will ultimately lead to new targets for the development of anti-TB drugs. In this work we present efforts towards the synthesis of initial peptide-based photo-affinity probe designs. The PAL probe has a modular design, consisting of the essential components for the labelling process: the affinity unit, which will bind to the native target; a photoactive group, which when activated by photolysis forms a reactive carbene that results in a covalent bond between the probe and target protein; and a reporter tag to assist separation and purification of the bound protein. 4, 5 These segments are synthesised in fragments and appended via peptide chemistry and biorthogonal click chemistry. Once synthesis of a small library of probes is complete, photoaffinity labelling of a Mycobacterium cell-free extract will be undertaken.

  1. Global tuberculosis report 2019. World Health Organization: Geneva, 2019.
  2. McLean, K. J.; Carroll, P.; Lewis, D. G.; Dunford, A. J.; Seward, H. E.; Neeli, R.; Cheesman, M. R.; Marsollier, L.; Douglas, P.; Smith, W. E.; Rosenkrands, I.; Cole, S. T.; Leys, D.; Parish, T.; Munro, A. W., Characterization of active site structure in CYP121. A cytochrome P450 essential for viability of Mycobacterium tuberculosis H37Rv. J Biol Chem 2008, 283 (48), 33406-16.
  3. Belin, P.; Le Du, M. H.; Fielding, A.; Lequin, O.; Jacquet, M.; Charbonnier, J. B.; Lecoq, A.; Thai, R.; Courçon, M.; Masson, C.; Dugave, C.; Genet, R.; Pernodet, J. L.; Gondry, M., Identification and structural basis of the reaction catalyzed by CYP121, an essential cytochrome P450 in Mycobacterium tuberculosis. Proc Natl Acad Sci U S A 2009, 106 (18), 7426-31.
  4. Murale, D. P.; Hong, S. C.; Haque, M. M.; Lee, J.-S., Photo-affinity labeling (PAL) in chemical proteomics: a handy tool to investigate protein-protein interactions (PPIs). Proteome Science 2017, 15 (1), 14.
  5. Liang, L.; Astruc, D., The copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) “click” reaction and its applications. An overview. Coordination Chemistry Reviews 2011, 255 (23), 2933-2945.