The effects of the sample matrix on the separation of peptides by HPCE has been investigated. Under both acidic and alkaline conditions, use of 25–30 mM salts in the sample zone resulted in much better resolution than did 100 mM salts. Prefocusing effects and acceleration of elution were also observed. These results agree well with the theory developed by Everaerts. In this paper a practical guide for high sensitivity, high resolution separation of salt‐containing peptide mixtures is proposed.
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