Potentiometric, UV and ¹H NMR study on the interaction of penicillin derivatives with Zn(II) in aqueous solution

The interaction of Zn(II) with ampicillin [(2S,5R,6R)-6-([(2R)-2-amino-2-phenylacetyl]amino)-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2- carboxylic acid] and amoxicillin [(2S,5R,6R)-6-{[(2R)-2-amino-2-(4-hydroxyphenyl)-acetyl]amino}-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-24-carboxylic acid] in NaCl aqueous solution at different ionic strengths and at t=25°C was investigated by potentiometric, UV and ¹H NMR techniques. Fairly similar speciation models were obtained for the two systems. At I=0.15molL^-1, two different sets of measurements, at low and high concentrations, were carried out. For the Zn²⁺-amoxicillin system, the Zn₂L₂(OH)₂ species was obtained in the set of measurements at high concentration. The spectrophotometric and ¹H NMR results thus obtained are fully consistent with the speciation models found from potentiometric investigations, confirming the formation as well as the relative stability of the complex species. The dependence of the stability constants on the ionic strength was modeled by means of the Debye-Hückel and SIT (Specific ion Interaction Theory) approaches, and the parameter that accounts for the variation of the stability constants with the ionic strength and the specific ion interaction parameters were determined for all the ionic species. The sequestering ability of the ligands towards Zn²⁺ was evaluated by determining the pL_0.5 parameter at different ionic strengths. It resulted that the sequestering ability of ampicillin is higher of ~0.5 order of magnitude with respect to amoxicillin.