Solution Equilibria between Aluminum(III) Ion and L-histidine or L-tyrosine

Toxic effects due to high aluminum body loads were observed in a number of conditions following ingestion of Al-containing antacids. Bio-availability of aluminum depends not only on the solubility of the ingested salt but also on the physico-chemical properties of the soluble Al complexes formed in body fluids. Amino acids may, upon interaction with Al-salts, form absorbable Al-complexes. Hence, complex formation equilibria between Al(3+) and either, L- histidine or L-tyrosine were studied by glass electrode potentiometric (0.1 mol/L LiCl ionic medium, 298 K), proton NMR and uv spectrophotometric measurements. Non linear least squares treatment of the potentiometric data indicates that in the concentration ranges: 0.5</=C(A1)</=2.0 ; 1.0</=C(His)</=10.0; 2.5</=PH</=6.5, in Al(3+) + His solutions, the following complexes (with log overall stability constants given in parenthesis) are formed: Al(HHis)(3+)(12.21+/-0.08); Al(His)(2+), (7.25+/-0.08); and Al(HHis)His(2+), (20.3+/-0.1). In Al(3+) + Tyr solutions in the concentration range 1.0</=C(Tyr)</=3.0 mmol/L and ligand to metal concentration ratio from 2:1 to 3:1, in the pH interval from 3.0 to 6.5 the formation of the following complexes was detected: Al(HTyr)(2+), (12.72+/-0.09); Al(Tyr)(2+), (10.16+/-0.03) and Al(OH)(2)Tyr , (2.70+/-0.05). Proton NMR data indicate that in Al(His)(2+) complex histidine acts as a monodentate ligand but its bidentate coordination is possible with carboxylate oxygen and imidazole 1-nitrogen as donors. In Al(HTyr)(3+) complex tyrosine is a monodentate ligand with carboxylate oxygen as donor. The mechanism of the formation of complexes in solution is discussed as well as their possible role in aluminum toxicity.