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Highly hydrophilic compounds belonging to biogenic amines were analysed in the reversed-phase system, modified with the addition of ionic liquids: 1-ethyl-3-methyl-imidazolium hexafluorophosphate (EMIM PF(6)) and chaotropic salt NaPF(6) on Discovery HS C18 column at acidic conditions. The effect of the additives concentration and the presence of organic solvent on the analytes' chromatographic parameters such as retention factor, tailing factor and theoretical plates number were all determined. On the basis of k versus ionic liquid concentration in aqueous-organic mobile phase with constant amount of phosphate buffer, retention mechanism was studied. It was established that the presence of organic solvent with low dielectric constant and ionic liquid with both chaotropic ions allows achieving typical Langmuir shape of this relationship. Investigated mobile phase additives are comparable according to efficiency and selectivity towards biogenic amines analysis. However, the sensitivity was found to be better for the eluent system modified with chaotropic salt.

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Sodium hexafluorophosphate, perchlorate and tetrafluoroborate were applied as the ion-pair reagents in reversed-phase chromatography of several imidazolium-based ionic liquids. The optimization of the retention was performed by changing the kind of organic modifier (methanol, acetonitrile), concentration and the kind of the ion-pair reagents in the mobile phase and the column kind (Zorbax SB-C18, Zorbax SB-Phenyl, Zorbax SB-CN, Zorbax SB-NH2 and Supelcosil LC-F). The selectivity of the proposed chromatographic systems according to the cation kind was compared on the basis of the resolution of ionic liquid mixture. The perturbation method was applied to identify the anion kind. The formation of ion-associated complexes between promethazine as counter-cation and chaotropic anions controlling their retention was confirmed.