Mass spectroscopy studies have established the existence of a new siderophore, Yel, a truncated version of yersiniabactin with a structure similar to pyochelin, a siderophore produced by Pseudomonas. In order to expand our understanding of the role of transition metals in infection pathogenesis and predict structure and reactivity of Yel complexes with metal cations, binding energies between Fe(III) and Zn(II) with Yel were calculated. Ground-state energies and frequencies of Yel, [Yel-Fe(III)]+ and Yel-Zn(II) complexes were calculated employing the Pople’s 6-311G** basis set. The performance of dispersion corrected B3LYP, PBE0, M06, M06-2X and wb97XD functionals was investigated. The effects of solvent were simulated using the Polarizable Continuum Model (PCM) with water as a solvent. Yel-M complexes have an octahedral structure with a 2:1 Yel/metal cation ratio. ZPE corrected Gibbs binding energies, calculated as the difference between the energies of reactants and product, are shown in Table 1. [Yel-Fe(III)]+ complexes are stable relatively to the Yel molecule, and binding energies are much higher than the ones for Ybt-Fe(III) complex (in the order of 200 kcal/mol), evincing the ability of iron binding of this novel siderophore. Zn(II) complexes, on the other hand, are unstable relatively to the Yel molecule. PCM simulations for the Yel molecule showed a stability increase of approximately 8 kcal/mol. Further studies will comprise the investigation of the binding energies of Yel-M complexes with M = Cu, Zn, Mn, Cr, Co, Ga, Ni.

DFT study of novel siderophore- metal complexes

2019 Spring National Meeting

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