Analytical and Bioanalytical Chemistry

, Volume 373, Issue 7, pp 618–627 | Cite as

Ligand and metal-ion effects in metal-ion clusters used for chiral analysis of α-hydroxy acids by the kinetic method

  • Lianming Wu
  • Andy W. Tao
  • R. Cooks
Special Issue Paper

Abstract

Chiral recognition of α-hydroxy acids has been achieved, and mixtures of enantiomers have been quantified in the gas phase, by using the kinetics of competitive unimolecular dissociation of singly-charged transition metal ion-bound trimeric complexes, [MII(A)(ref*)2–H]+ (MII=divalent transition metal ion; A=α-hydroxy acid; ref*=chiral reference ligand), to form the dimeric complexes [MII(A)(ref*)–H]+ and [MII(ref*)2–H]+. Chiral selectivity, the ratio of these two fragment ion abundances for the complex containing the analyte in one enantiomeric form expressed relative to that for the fragments of the corresponding complex containing the other enantiomer, ranges from 0.65 to 7.32. Chiral differentiation is highly dependent on the choice of chiral reference compound and central metal ion. The different coordination geometry of complexes resulting from the different d-orbital electronic configurations of these transition metal ions plays a role in chiral discrimination . Of all the transition metal ions examined chiral recognition is lowest for CuII, because of large distortion of the coordination complexes, and hence weak metal–ligand interactions and small stereochemical effects. It seems that two independent π-cation interactions occur when N-acetyl-substituted aromatic amino acids used as the reference ligands and this accounts for improved chiral discrimination. If both metal–ligand and ligand–ligand interactions are optimized, large chiral selectivity is achieved. The sensitive nature of the methodology and the linear relationship between the logarithm of the fragment ion abundance ratio and the optical purity, which are intrinsic to the kinetic method, enable mixtures to be analyzed for small enantiomeric excess (ee) by simply recording the ratios of fragment ion abundances in a tandem mass spectrum.

α-Hydroxy acids Chiral analysis Kinetic method Tandem mass spectrometry Electrospray ionization Transition metal-bound complexes 

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Copyright information

© Springer-Verlag 2002

Authors and Affiliations

  • Lianming Wu
    • 1
  • Andy W. Tao
    • 1
  • R. Cooks
    • 1
  1. 1.Department of Chemistry, Purdue University, West Lafayette, IN 47907USA
  2. 2.Current address: Institute for Systems Biology, 1441 North 34th Street, Seattle, WA 98103USA

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