On capillary ion-exchange preconcentration of inorganic anions in open-tubular capillary electrochromatography with elution using transient-isotachophoretic gradients. 2. Characterization of the isotachophoretic gradient
Mc. Breadmore et al., On capillary ion-exchange preconcentration of inorganic anions in open-tubular capillary electrochromatography with elution using transient-isotachophoretic gradients. 2. Characterization of the isotachophoretic gradient, ANALYT CHEM, 73(4), 2001, pp. 820-828
Diffuse transient-isotachophoretic boundaries can be used as an elution gra
dient of increasing eluotropic strength to elute inorganic anions that have
been preconcentrated on an open-tubular ion-exchange stationary phase prio
r to electrophoretic separation. The generation and characteristics of thes
e gradients for elution after preconcentration have been investigated. The
gradients are generated by placing a low-mobility, weak ion-exchange compet
ing anion in the capillary (weak electrolyte, WE), and a high-mobility, str
ong ion-exchange competing anion in the electrolyte vials (strong electroly
te, SE), Application of voltage establishes a diffuse boundary with the com
position changing from the weak anion to the strong anion, Comparison of el
ution gradients generated with different electrolyte systems was accomplish
ed by comparing the eluotropic strength (a function of eluent concentration
, ion-exchange selectivity coefficient, and charge) and the shape of the pr
ofile as it changes from WE to SE. The ion-exchange selectivity coefficient
of the SE competing anion is important in establishing a sharp change in e
lution strength. A large difference in mobility between the WE and SE compe
ting anions gives an SE with a higher final eluotropic strength, but the sl
ope of the gradient is shallower. This results in a reduction in the effici
ency of analyte focusing. To ensure maximum focusing efficiency, the WE and
SE electrolytes should be selected such that the SE has the highest possib
le eluotropic strength for a given concentration of WE. The SE competing an
ion should also have a sufficiently low electrophoretic mobility to ensure
focusing for the maximum number of analytes, and the mobility difference be
tween the WE and SE competing anions should be as small as possible.