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Ligand Exchange Chromatography: History
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Contributor: Helena Kang

Analyte molecules that displace ligands from a metal center immobilized on a chelating stationary phase, or that coordinate to a metal ion in the eluent, constitute ligand-exchange chromatography (LEC). The metal—commonly Cu(II), Zn(II), or a surface metal on zirconia—presents vacant coordination sites; solutes with donor atoms (amino acids, sugars, enantiomeric drugs) form transient complexes whose stability constants differ, and those differences become chromatographic selectivity [1]. Chiral LEC uses a chiral ligand or a chiral mobile-phase additive around the metal to resolve enantiomers [2]. Conceptual boundaries exclude immobilized-metal affinity chromatography that captures histidine-tagged proteins on Ni(II) or Co(II) without a ligand-exchange elution of small donor solutes as the defining mode, and they exclude ordinary ion-exchange chromatography. Essential features are a defined metal–ligand coordination sphere, reversible exchange of that sphere with the analyte, and a mobile phase that supplies competing ligands or protons to release the solute [3]. Lewis acid–base binding of carboxylates on zirconia is a related ligand-exchange process on an oxide surface [4].

  • ligand-exchange chromatography
  • metal coordination
  • chiral ligand exchange
  • chelating phase

Analytical Chemistry and Chromatography • Spectroscopy • Chemistry • Physical Sciences

References

  1. Alvin Siegel; Egon T. Degens; Concentration of Dissolved Amino Acids from Saline Waters by Ligand-Exchange Chromatography. Sci. 1966, 151, 1098-1101, 10.1126/science.151.3714.1098.
  2. Wentao Bi; Minglei Tian; Kyung Ho Row; Chiral separation and determination of ofloxacin enantiomers by ionic liquid-assisted ligand-exchange chromatography. Anal. 2010, 136, 379-387, 10.1039/c0an00657b.
  3. Hongyuan Yan; Kyung Ho Row; Rapid chiral separation and impurity determination of levofloxacin by ligand-exchange chromatography. Anal. Chim. Acta 2007, 584, 160-165, 10.1016/j.aca.2006.11.023.
  4. John A. Blackwell; Peter W. Carr; The role of Lewis acid-base processes in ligand-exchange chromatography of benzoic acid derivatives on zirconium oxide. Anal. Chem. 1992, 64, 853-862, 10.1021/ac00032a007.
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