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 calo...

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Veröffentlicht in:Chirality (New York, N.Y.) N.Y.), 1997, Vol.9 (4), p.341-349
Hauptverfasser: Bonomo, Raffaele P., Cucinotta, Vincenzo, D'Alessandro, Franca, Impellizzeri, Giuseppe, Maccarrone, Giuseppe, Rizzarelli, Enrico, Vecchio, Graziella, Carima, Lorenza, Corradini, Roberto, Sartor, Giorgio, Marchelli, Rosangela
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container_title Chirality (New York, N.Y.)
container_volume 9
creator Bonomo, Raffaele P.
Cucinotta, Vincenzo
D'Alessandro, Franca
Impellizzeri, Giuseppe
Maccarrone, Giuseppe
Rizzarelli, Enrico
Vecchio, Graziella
Carima, Lorenza
Corradini, Roberto
Sartor, Giorgio
Marchelli, Rosangela
description 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. Chirality 9:341–349, 1997. © 1997 Wiley‐Liss, Inc.
doi_str_mv 10.1002/(SICI)1520-636X(1997)9:4<341::AID-CHIR5>3.0.CO;2-G
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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. Chirality 9:341–349, 1997. © 1997 Wiley‐Liss, Inc.</description><identifier>ISSN: 0899-0042</identifier><identifier>EISSN: 1520-636X</identifier><identifier>DOI: 10.1002/(SICI)1520-636X(1997)9:4&lt;341::AID-CHIR5&gt;3.0.CO;2-G</identifier><identifier>PMID: 9275313</identifier><language>eng</language><publisher>New York: Alan R. 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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. 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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. Chirality 9:341–349, 1997. © 1997 Wiley‐Liss, Inc.</abstract><cop>New York</cop><pub>Alan R. Liss, Inc</pub><pmid>9275313</pmid><doi>10.1002/(SICI)1520-636X(1997)9:4&lt;341::AID-CHIR5&gt;3.0.CO;2-G</doi><tpages>9</tpages></addata></record>
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subjects Alanine - chemistry
amino acids
Aminopyridines - chemical synthesis
Aminopyridines - chemistry
beta-Cyclodextrins
Calorimetry
chiral recognition
Chromatography, High Pressure Liquid
Circular Dichroism
Copper - chemistry
Cyclodextrins - chemical synthesis
Cyclodextrins - chemistry
Electron Spin Resonance Spectroscopy
EPR
fluorescence
Magnetic Resonance Spectroscopy
Molecular Conformation
Potentiometry
Spectrometry, Fluorescence
Spectrophotometry, Ultraviolet
stability constants
Stereoisomerism
ternary copper(II) complexes
Thermodynamics
Tryptophan - chemistry
title Chiral recognition by the copper(II) complex of 6-deoxy-6-N-(2-methylaminopyridine)-β-cyclodextrin
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