Identification of complexes containing glutathione with As(III), Sb(III), Cd(II), Hg(II), Tl(I), Pb(II) or Bi(III) by electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry (ESI-MS) of mixtures containing glutathione (GSH) and nitrates, oxides or chlorides of the heavy metals, arsenic, antimony, cadmium, mercury, thallium, lead or bismuth allows for definitive identification of complexes in the gas phase. In the positive ion mode, spectra show prominent m/z peaks that are assigned to monocations of general formulae [E(GSH) - xH](+)(E = Cd, Hg, TI, Pb, As, Sb or Bi; x = 0, 1 or 2), [E(GSH)(2) - xH](+) (E = Hg, As, Sb, or Bi; x = 1 or 2), [E(GSH)3 - xH]+ (E = As, Sb or Bi; x = 2), [E2(GSH) - xH]+ (E = TI or Pb; x = 1 or 3), [E-2(GSH)(2) - xH]+ (E = Bi; x = 5), [E-2(GSH)(3) - xH](+) (E = Bi; x = 5), and/or [E-3(GSH) - xH](+) (E = TI; x = 2). Spectra obtained in the negative ion mode give m/z peaks observed in assigned to monoanionic species that correspond to some of the monocationic species listed above with two protons removed. The results demonstrate the potential application of ESI-MS as a versatile and efficient approach to study toxic heavy metals in biological systems. In addition, the observations provide a foundation database to understand the chemistry of these heavy metals with bio-molecules. (c) 2005 Elsevier Inc. All rights reserved.