Peak-shape correction to symmetry for pressure-driven sample injection in capillary electrophoresis.

Pressure-driven sample injection in capillary electrophoresis results in asymmetric peaks due to difference in shapes between the front and the back boundaries of the sample plug. Uneven velocity profile of fluid flow across the capillary gives the front boundary a parabolic shape. The back side, on the other hand, has a flat interface with the electrophoresis run buffer. Here, we propose a simple means of correcting this asymmetry by pressure-driven "propagation" of the injected plug, with the parabolic sample-buffer interface established at the back. We prove experimentally that such a propagation procedure corrects peak asymmetry to the level comparable to injection through electroosmosis. Importantly, the propagation-based correction procedure also solves a problem of transferring the sample into the efficiently cooled zone of the capillary for capillary electrophoresis (CE) instruments with active cooling. The suggested peak correction procedure will find applications in all CE methods that rely on peak shape analysis, e.g., nonequilibrium capillary electrophoresis of equilibrium mixtures.