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. 2002;8(5):235–248. doi: 10.1155/MBD.2002.235

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

Predrag Djurdjevic 1,, Ratomir Jelic 1, Dragana Dzajevic 1, Mirjana Cvijovic 2
PMCID: PMC2365283  PMID: 18476000

Abstract

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 Al3+ 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≤CA1≤2.0 ; 1.0≤CHis≤10.0; 2.5≤PH≤6.5, in Al3+ + 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)His2+, (20.3±0.1). In Al3+ + Tyr solutions in the concentration range 1.0≤CTyr≤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)2Tyr , (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.

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