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Updated: Apr 23, 2026

A Study of the Complexation of MercuryII with Dicysteinyl Tetrapeptides by Electrospray Ionization Mass Spectrometry
Published on: January 8, 2016
Theoretical spectroscopic studies and identification of metal-citrate (Cd and Pb) complexes by ESI-MS in aqueous
Alexandre C Bertoli1, Ruy Carvalho1, Matheus P Freitas1
1Departamento de Química, Universidade Federal de Lavras, Caixa Postal 3037, 37200-000 Lavras, MG, Brazil.
Abstract:
The combined use of ESI-MS, FTIR-ATR and theoretical calculations for the determination of metal-citrate (metal=Cd and Pb) structures are reported. Mass spectrometry allowed to determine the stoichiometry 1:1 and 2:1 of the complexes, corroborating the theoretical calculations. The species found in the ratio 2:1 had their molecular structures readjusted, since the deprotonation of citric acid differed from what was simulated. The calculations of thermodynamic stability (ΔH(0)(aq.)) for the complexes obtained by B3LYP/LANL2DZ were more exoenergetic than those found by PM6. However, for both methods, the stability of the complexes follows a trend, that is, the lowest-energy isomers in PM6 are also the most stable in B3LYP/LANL2DZ. The infrared analysis suggested that carboxyl groups are complexation sites and hydrogen bonds can help in the stability of the complexes. The vibrational frequencies in B3LYP/LANL2DZ had a good correlation with the experimental infrared results.
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