Non-covalent interactions in thermodynamic stereoselectivity of mixed-ligand copper(II)-D- or L-histidine complexes with L-amino acids. A possible model of metal ion-assisted molecular recognition

Abstract

Formation constants of ternary complexes of copper(II), L/D-histidine and, in turn, glycine, L-alanine, L-valine, L-leucine, L-tryptophan, or L-phenylalanine have been determined potentio-metrically at 25 °C and I= 0.1 mol dm–3(KNO3). In the case of amino acids with aromatic side chains the ternary complexes containing ligands of opposite chirality are more stable than those having ligands of the same chirality; the opposite is true for amino acids with aliphatic residues. Calorimetric measurements have been carried out to obtain the enthalpy and entropy values associated with complex formation. Copper(II)–histamine ternary systems with L-alanine or L-phenylalanine have also been investigated. Comparison of the thermodynamic parameters pertinent to formation of the histamine complexes with those of the analogous histidine complexes allows one to ascertain the number of donor atoms involved in the co-ordination to copper(II), in the histidine systems. The determination of ΔH⊖ and ΔS⊖ values renders easier understanding of the factors determining Stereoselectivity in the above systems. The Stereoselectivity may be explained in terms of non-covalent interactions between side-chain residues. The role played by the histidine carboxylate in the molecular recognition of amino acids is also discussed.