Keywords: Amino Acids, Chiral Recognition, Circular Dichroism, Fluorescence, Stability Constants, Ternary Copper(ii) Complexes, Aromatic Amino Acid, Beta Cyclodextrin Derivative, Glycinate Copper, Article, Binding Site, Calorimetry, Chirality, Conformation, Electron Spin Resonance, Enantiomer, High Performance Liquid Chromatography, Potentiometry, Priority Journal, Proton Nuclear Magnetic Resonance, Proton Transport, Stereochemistry, Thermodynamics, Alanine, Aminopyridines, Beta-Cyclodextrins, High Pressure Liquid, Electron Spin Resonance Spectroscopy, Magnetic Resonance Spectroscopy, Molecular Conformation, Spectrometry, Spectrophotometry, Ultraviolet, Stereoisomerism, Tryptophan, Ternary Copper (ii) Complexes,
Affiliations: Dipartimento di Scienze Chimiche, Universitè di Catania, Catania, Italy
Dipto. di Scienze degli Alimenti, Univ. Federico II di Napoli, Napoli, Italy
Ist. Stud. Sostanze Naturali I., CNR, Catania, Italy
Dipto. di Chim. Organ. e Industriale, Università di Parma, Parma, Italy
Istituto di Chimica Biologica, Università di Parma, Parma, Italy
References: Not available.
Chiral recognition by the copper(ii) complex of 6-deoxy-6-n-(2 - methylaminopyridine)-β-cyclodextrin
A modified β-cyclodextrin bearing a 2-aminomethylpyridine binding site for copper (II) (6-deoxy-6-[N-(2-methylamino)pyridine)]-β-cyclodextrin, CDampy) was synthesized by C6-monofunctionalization. The acid-base properties of the new ligand in aqueous solution were investigated by potentiometry and calorimetry, and its conformations as a function of pH were studied by NMR and circular dichroism (c.d.). The formation of binary copper(II) complexes was studied by potentiometry, EPR, and c.d.. The copper(II) complex was used as chiral selector for the HPLC enantiomeric separation of underivatized aromatic amino acids. Enantioselectivity in the overall stability constants of the ternary complexes with D- or L-Trp was detected by potentiometry, whereas the complexes of the Ala enantiomers did not show any difference in stability. These results were consistent with a preferred cis coordination of the amino group of the ligand and of the amino acid in the ternary complexes ('cis effect'), which leads to the inclusion of the aromatic side chain of D-Trp, but not of that of L-Trp. In Trp-containing ternary complexes, the two enantiomers showed differences in the fluorescence lifetime distribution, consistent with only one conformer of D-Trp and two conformers of L-Trp, and the latter were found to be more accessible to fluorescence quenching by acrylamide and KI.
Chiral recognition by the copper(ii) complex of 6-deoxy-6-n-(2 - methylaminopyridine)-β-cyclodextrin
Kállay C, Dávid A, Timári S, Nagy EM, Sanna D, Garribba E, Micera G, De Bona P, Pappalardo G, Rizzarelli E, Sóvágó I * Copper(II) complexes of rat amylin fragments(572 views) Dalton T (ISSN: 1477-9234, 1477-9226, 1477-9234electronic), 2011 Oct 14; 40(38): 9711-9721. Impact Factor:3.838 ViewExport to BibTeXExport to EndNote