Abstract
Method to calculate micellar phase residence time [tmic = tmc k‴, time spent by the analyte in the micellar phase] and aqueous phase residence time [taq, = t0 (1 − k‴), time spent by the analyte in the aqueous phase] was developed, where tm, to and tmc are the migration time of the analyte, the flow marker and the micelles, respectively. It was proved that migration time of the analyte is the sum of the phase residence times [tm = tmic + taq = t0 (1 − k‴) + k‴ tmc]. Two physico-chemical parameters characterizing hydrophobicity of the analyte, namely the ratio of the moles of the analyte in the micellar (nmc) and aqueous (naq) phase (nmc/naq = tmic/taq) as well as distribution coefficient (K) have also been determined from the phase residence times. Good correlation was found between the micellar phase residence times and computer calculated hydrophobicity values (S) in the case of hydroxy- and aldehyde benzene derivatives, benzene- and alkyl phenone homolog series and in the case of seven hydrophobic protected peptides. Comparison of hydrophobicity values and phase residence times showed that the higher the hydrophobicity of the analyte the longer the time spent in the micellar (hydrophobic) phase. The micellar phase residence time determinable experimentally in MEKC reflects the hydrophobicity of the molecule investigated.
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