Proton-Ionizable Crown Compounds: Transport of Alkali and Alkaline Earth Cations Using Proton-Ionizable Triazolo Macrocycles

Abstract
The macrocycle-mediated flaxes of the alkali and alkaline earth metal cations have been determined in a H2O-CH2Cl2-H2O bulk liquid membrane system. Water-insoluble proton-ionizable macrocycles of the triazolo type were used. The proton-ionizable feature allows the coupling of cation transport to reverse H+ transport. This feature offers promise for the effective separation and/or concentration of alkali metal ions with the metal transport being driven by a pH gradient. A counter anion in the source phase is not co-transported. Transport of the alkali cations only occurred when the source phase pH was greater than the aqueous pKa value for the carriers. Transport increased regularly with increasing source phase pH. Transport of alkaline earth cations from neutral pH source phases was minimal. The alkali cation selectivity order was K+ > Rb+ > Cs+ > Na+ > Li+ for the l8-crown-6 sized macrocycles, while little selectivity was observed with the 15-crown-5 sized macro-cycle.

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