The migration behavior and selectivity of thirteen sulfonamides in cap
illary electrophoresis (CE), with emphasis on micellar electrokinetic
chromatography (MEKC) were systematically investigated using a phospha
te-borate buffer electrolyte, with sodium dodecyl sulfate (SDS) as an
anionic surfactant in MEKC. The optimization strategies for the separa
tion of sulfonamides in capillary zone electrophoresis (CZE) and in ME
KC are described. The migration behavior and selectivity of sulfonamid
es in CZE are mainly manipulated by the pH of the buffer. The migratio
n order of sulfonamides depends on the ratios of charge to mass (q/M-2
/3) and is primarily determined by their pK(a) values. Thus precise op
timization of buffer pH is crucial to further improve the separation o
f some closely migrating sulfonamides. On the other hand, buffer pH an
d micelle concentration greatly affect the migration and selectivity o
f sulfonamides in MEKC. The migration order of sulfonamides is mainly
determined by their pK(a) values and the magnitude of the binding cons
tants of solutes-to-micelles. The influences of buffer pH and micelle
concentration correlate with each other. The magnitude of the binding
constants correlates with the differences between the electrophoretic
mobility of sulfonamides measured at a pH below pK(a)-2 in CZE and tha
t in MEKC. In this work, acid dissociation constants of these sulfonam
ides and binding constants of sulfonamides to SDS micelles in a phosph
ate-borate buffer are reported. (C) 1997 Elsevier Science B.V.