Dx. Zhang et al., Chiral resolution of D- and L-amino acids by tandem mass spectrometry of Ni(II)-bound trimeric complexes, INT J MASS, 204(1-3), 2001, pp. 159-169
Mass-selected trimeric cluster ions, [Ni-11(A)(ref*)(2)-H](+), where A desi
gnates the analyte amino acid and ref* designates the chiral reference amin
o acid, undergo competitive collision-induced dissociation to yield two dim
eric clusters with a branching ratio dictated by the stereochemistry of bot
h the analyte and the reference. This branching ratio (R) is related, using
the kinetic method, to an enthalpic term, Delta (NiBDE)-B-11, the differen
ce between the formation enthalpies of the two dimeric clusters. Chiral res
olution of (D)- acid (L)-amino acids is directly related to the relative st
abilities of the two diastereomeric clusters formed by the dissociation of
the Ni(II)-bound trimeric clusters. The dimeric product ions differ in enth
alpy by only a few kilojoules per mole, but chiral recognition is achieved
for all 19 naturally occurring chiral amino acids, using appropriate refere
nce amino acids. Because there is evidence that the dissociating trimeric d
usters may exist in different isomeric forms, the proportion of analyte ver
sus reference amino acids in the mixture was examined to study the effect o
f this ratio on the success of chiral recognition. The effect was found to
be negligible. This suggests that there is an equilibrium between these iso
meric clusters, which is governed by thermochemical properties rather than
the relative concentrations of the constituent amino acids. A linear correl
ation was observed between In(R) and enantiomeric compositions of the analy
te as expected from the kinetic method treatment, acid the direct measureme
nt of optical purity to within 3% enantiomeric excess was demonstrated. Wit
h this new chiral recognition technique, qualitative and quantitative chira
l analysis of amino acids is achieved. (C) 2001 Elsevier Science B.V.