Separation of a number of transition metal complexes with bis(2-hydroxyethy
l)dithiocarbamate (HEDTC) by micellar electrokinetic capillary chromatograp
hy (MEKC) with direct photometric detection was investigated. Pre-capillary
complexation was shown to be superior to on-capillary complexation in term
s of the number of metals ions which could be detected and their peak shape
s, enabling analysis of Cd(II), Pb(II), Pt(II), Co(II), Ni(II), Bi(III), Cr
(II), Cu(II) and Hg(II). The type and composition of the background electro
lyte (BGE) were investigated with respect to separation selectivity and BGE
stability. A BGE of 60 mM 3-(morpholino)propane sulfonic acid (MOPS), 30 m
M tris(hydroxymethyl)aminomethane (Tris), 10 mM sodium dodecyl sulphate (SD
S) and 100 mu M HEDTC, pH 7.2 was found to be optimal with nine metals base
line separated in less than seven minutes, and giving separation efficienci
es of up to 367 000 theoretical plates, reproducibility of corrected peak a
reas below 3% relative standard deviation, concentration detection limits f
rom 0.04 to 1.3 mu M and mass detection limits at sub femtomole levels (det
ection at 254 nm).