On-column fluorescence labeling using hydrophobic probe molecules is d
escribed for the enhancement of detection in capillary zone electropho
resis (CZE) and micellar electrokinetic capillary chromatography (MECC
). Experimental details are presented for the detection of alkyl sulfa
te surfactant/micelle systems using the probe 2-p-toluidinonaphthalene
-6-sulfonate. Using this labeling scheme, laser fluorimetry is employe
d to determine sodium dodecyl sulfate in a generic, commercial soap pr
oduct. The influence of probe molecule concentration on calibration pl
ots and analyte mobility is also presented. The utility of indirect de
tection for MECC is demonstrated with the addition of 1-anilinonaphtha
lene-8-sulfonate to the micellar mobile phase. A brief discussion of t
he analytical merits of this mode of detection is presented.