Capillary electrophoresis, free solution amino acids

Jorgenson reported the use of glass capillaries for free solution electrophoresis 25 years ago (Jorgenson andLukacs, 1981,1983). Aplug of analyte was introduced into a buffer-filled capillary and separated at high electric fields. Capillaries of 75 im inner diameter were employed, and detection of labeled amino acids and peptides was based on fluorescence. 

The reversal of the direction of the electro-osmotic flow by the adsorption onto the capillary wall of alky-lammonium surfactants and polymeric ion-pair agents incorporated into the electrolyte solution is widely employed in capillary zone electrophoresis (CZE) of organic acids, amino acids, and metal ions. The dependence of the electro-osmotic mobility on the concentration of these additives has been interpreted on the basis of the model proposed by Fuerstenau [6] to explain the adsorption of alkylammonium salts on quartz. According to this model, the adsorption in the Stern layer as individual ions of surfactant molecules in dilute solution results from the electrostatic attraction between the head groups of the surfactant and the ionized silanol groups at the surface of the capillary wall. As the concentration of the surfactant in the solution is increased, the concentration of the adsorbed alkylammonium ions increases too and reaches a critical concentration at which the van der Waals attraction forces between the hydrocarbon chains of adsorbed and free-surfactant molecules in solution cause their association into hemimicelles (i.e., pairs of surfactant molecules with one cationic group directed toward the capillary wall and the other directed out into the solution). 

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