A dynamic model is presented for simulation of reaction-based chemical
analysis of enzymes and substrates in capillary electrophoretic syste
ms by the methodology of electrophoretically mediated microanalysis (E
MMA). The mathematical model utilizes mass balance expressions describ
ing the time-dependent effects of electromigration, chemical reaction,
and diffusional band broadening upon the concentration profiles of th
e various reagent and product species. The model is implemented in an
iterative computer program in which the capillary is segmented into ar
rays of bins storing the concentration profiles of each of the chemica
l species. During each time increment, the effects of electrophoresis,
reaction kinetics, and diffusion are calculated, and the concentratio
ns stored in the arrays are updated. The flexibility of the model to a
ccommodate various initial capillary conditions, sample introduction m
ethods, and voltage programming allows diverse EMMA analyses to be sim
ulated. The simulated results are shown to be in good qualitative agre
ement with experimental data for zonal injection and moving boundary E
MMA determinations of leucine aminopeptidase as well as an EMMA analys
is of ethanol.