Electromigration dispersion (EMD) is a common problem in the electromigration separation methods. The dispersion of the analyte peak can significantly lower the resolution or even disable the separation.
There are several computational programs enabling the prediction of EMD in non-complexing separation systems, but the model for systems with complexation agents is still missing. Therefore, we present the complete theory of EMD in electrophoretical systems with fully charged analytes and neutral complexation agents.
This theory was implemented into the newest version of our simulation program PeakMaster 5.3. Thus, we are able to calculate the relative velocity slope S-x, which is usually used as a measure of EMD.
The established theory was tested by both experiments and simulations, which were performed by our simulation program Simul 5 Complex, using 3 different chiral separation systems. The values of relative velocity slopes were calculated from both experimental and simulated data and compared with those predicted by PeakMaster 5.3 Complex.
The perfect agreement of the data was achieved. The obtained results were also used to explain the development of EMD in systems with complexing agents.
As a result, we propose a way to avoid EMD, get sharp and symmetrical analyte peaks, and thus, maximize resolution.